Fungicides with triazole groups and oligo ethers

The invention relates to a liquid composition, for the protection of vegetables, in particular, in the fight against parasitic fungi, being effective in regulating the growth of vegetables.

It is known that, in the literature, a number of compounds of the triazole group are already described, in particular, with fungicidal action.

The aim of the invention is to expand the range of compounds that have a clear activity, in particular, against some plant diseases, such as rust, Oidium parasitic fungus and in particular against parasitic Oidium fungi. to cereals.

The problem solved by the invention consists in the association, in certain proportions, of a new active substance with surfactants and solvents, in order to obtain a plant protection composition.

The composition according to the invention consists of 2.5 - 4 parts of compounds of general formula I:

<img file="RO91074A_D0001.tif" />

(I)

W ', wherein X represents a halogen atom, preferably fluorine, bromine or chlorine or a cyano or nitro group or an alkyl or alkoxy group having 1 to 12 atoms. ₁₅ of carbon, preferably from 1 to 4 carbon atoms, these groups possibly being monohalogenated or polyhalogenated, especially preferring the CF group₃, n represents an integer, between 0 and 6, of price²⁰ a ference equal to two, being understood that when n is greater than 1, the substituents of X can be either identical or different, W represents a trivalent group ---CH-, or a nitrogen atom == N -, R₂ represents a

LAW PRICE 94.31

I hydrogen atom or an alkyl radical having 1 ... 4 carbon atoms, R₂ represents a hydrogen atom or a 1-4 alkyl carbon atom, cycloalkyl with

5 ... 7 carbon atoms, phenyl or phenylalkyl optionally substituted by halogen, preferably chlorine and fluorine with alkoxy and phenyloxy groups, 0.4 ... 1.25 parts of surfactant selected from sodium dodecylbenzenesulfonate, condensed with nonylphenol with 10: 1 ethylene oxide, epoxidized vegetable oil or mixture of alkyl arylsulfonates and polyglycol ethers and fatty alcohols and 6.25 ... 10 parts solvent selected from cyclohexane, dimethylformamide, and aromatic solvents.

The following are two examples of embodiments of the invention.

Example 1. 400 g active substance, 24 g alkaline dodecylbenzene sulfonate, 16 g ethylene oxide nonylphenol condensate 10: 1, 200 g cyclohexanonone, and aromatic solvent as needed up to 1 liter of concentrate.

Example 2. 250 g active substance, 25 g epoxidized vegetable oil, 100 g mixture of alkylarylsulfonate and polyglycolic ether and fatty alcohols, 50 g dimethylformamide and 575 g xylene.

Starting from these concentrates can be obtained by dilution with water, emulsions of any desired concentration that are particularly suitable for application on the leaves.

Concentrated suspensions, equally applicable by spraying, are prepared in such a way as to obtain a stable fluid product that will not be stored and generally contain from 10 to 75% active material, from 0.5 in 15% of surfactants, from 0.1 to 10% of thixotropic agents from 0 to 10% of suitable additives such as, for example, anti-foaming agents, corrosion inhibitors, stabilizers, penetration agents and adhesives as well as support substances, water or an organic liquid in which the active matter is slightly soluble or insoluble; such organic solids or mineral salts may be dissolved in support substances to prevent sedimentation or as antifreeze for water.

Table 1 illustrates the compounds according to the present invention. Among the physical properties indicated for these compounds,²⁰ the displacement values ​​(delta) in the nuclear magnetic resonance spectrum of the proton in the group - C-CIT-O (acetal) - are indicated. These trips are measured in parts per million and they are represented²⁵ relative to a surface product which is tetramethyl silane. Spectroscopic analysis of nuclear magnetic resonance is performed at one hundred megahertz₃₀ deuterated chloroform medium.

Methods for testing compounds according to the invention are indicated below.

Table 1

<td>compound No</td><td>X¹</td><td>R¹</td><td>R²</td><td>Diastereolsomers</td><td>ft</td><td>delta (NMR)</td>

<td>1 (ex. 1)</td><td>H</td><td>H</td><td>ch₃</td><td>A + B</td><td>oil</td><td> 5,15 5,02</td>

<td> 2</td><td>H</td><td>H</td><td>c₂h₅—</td><td>A</td><td> 88</td><td> 5,27</td>

<td> 3</td><td>H</td><td>H</td><td>c₂h₅—</td><td>B</td><td>oil</td><td> 5,14</td>

<td> 4</td><td>H</td><td>H</td><td>n-GgHŢ-</td><td>A</td><td>oil</td><td> 5,26</td>

<td> 5</td><td>H</td><td>H</td><td>nC₃H -</td><td>B</td><td>oil</td><td> 5,12</td>

<td> 6</td><td>H</td><td>H</td><td>nC₄H₉-</td><td>A + B</td><td>oil</td><td> 5,25 5,11</td>

<td> 7</td><td>H</td><td>H</td><td>I20-C₃Hj-</td><td>A</td><td>oil</td><td> 5.39</td>

<td> 8</td><td>H</td><td>H</td><td>Iso CGTTT ··</td><td>B</td><td> 70</td><td> 5,24</td>

<td> 9</td><td>Cl</td><td>H</td><td>ch₃-</td><td>A + B</td><td>oil</td><td> 5,20 5,04</td>

<td>10 (ex. 2)</td><td>Cl</td><td>H</td><td>c₂h₅-</td><td>A</td><td> 61</td><td> 5,30</td>

<td>11 (ex. 2)</td><td>Cl</td><td>H</td><td>c₂h₅-</td><td>B</td><td> 164</td><td> 5,14</td>

<td> 12</td><td>Cl</td><td>H</td><td>nC₃Hj-</td><td>A + B</td><td>oil</td><td> 5,14 5,31</td>

<td> 13</td><td>Cl</td><td>H</td><td>nC₃H₇-</td><td>A</td><td>oil</td><td> 5,31</td>

<td> 14</td><td>Cl</td><td>H</td><td>nC₃H₇-</td><td>B</td><td> 116</td><td> 5,14</td>

Table 1 (continued)

<td>compound Nr.</td><td>X¹</td><td>Ri</td><td>R *</td><td>Oizomeri diastere</td><td>pt</td><td>delta (NMR)</td>

<td> 1 15</td><td>Cl</td><td>H</td><td>Iso G3H7-</td><td>A</td><td> 100</td><td> 5,42</td>

<td> 16</td><td>Cl</td><td>H</td><td>iso-C₃H₇-</td><td>B</td><td> 149</td><td> 5,26</td>

<td> 17</td><td>Cl</td><td>H</td><td>nC₄H₉-</td><td>Λ (85%)</td><td>oil</td><td> 5,30</td>

<td> 18</td><td>Cl</td><td>H</td><td>nC₄H₉-</td><td>B (90%)</td><td>oil</td><td> 5,14</td>

<td> 19</td><td>Cl</td><td>H</td><td>nC₅H_u-</td><td>A (60%)</td><td>oil</td><td> 5,30</td>

<td> 20</td><td>Cl</td><td>H</td><td>nC₆H_u-</td><td>B (90%)</td><td>oil</td><td> 5,13</td>

<td> 21</td><td>Cl</td><td>H</td><td>C1-CH₃CH₃-</td><td>A</td><td> 103</td><td> 5,35</td>

<td> 22</td><td>Cl</td><td>H</td><td>but-ch₂-but it₂-</td><td>B</td><td> 135</td><td> 5,19</td>

<td> 23</td><td>Cl</td><td>H</td><td>cyclohexyl</td><td>A + B</td><td>oil</td><td> 5,47 5,31</td>

<td> 24</td><td>Cl</td><td>H</td><td>cyclohexyl</td><td>B</td><td> 118</td><td> 5,31</td>

<td> 25</td><td>Cl</td><td>H</td><td>p-Cl-C₆H₄-O-CH_ofCH₂-</td><td>A</td><td>oil</td><td> 5,39</td>

<td> 26</td><td>Cl</td><td>H</td><td>p-Cl-C₆H₄-O-CH₂CH₂-</td><td>B</td><td> 128</td><td> 5,22</td>

<td> 27</td><td>Cl</td><td>HC1₃</td><td>nC₄II₉-</td><td>A + B + C + D</td><td>oil</td><td></td>

<td> 28</td><td>Cl</td><td>CH₃</td><td>CH₃-</td><td>A + B + C + D</td><td>oil</td><td> 4,90/4,74 4,74/4,55</td>

<td> 29</td><td>Cl</td><td>ch₃</td><td>c₂h₅-</td><td>A + B + C + D</td><td>oil</td><td> 5,01/4,84 4,82/4,62</td>

<td> 30</td><td>Cl</td><td>ch₃</td><td>nC₃H₇-</td><td>A + B + C + D</td><td>oil</td><td> 5,01/4,83 4,81/4,60</td>

<td> 31</td><td>Cl</td><td>η-ΟβΗϊ-</td><td>ch₃</td><td>A + B + C + D</td><td>oil</td><td></td>

<td> 32</td><td>Cl</td><td>nC₃H₇-</td><td>c₂h₅-</td><td>A + B + C + D</td><td>oil</td><td></td>

<td> 33</td><td>Cl</td><td>H</td><td>iso-C₄H₉-</td><td>A</td><td> 71°</td><td> 5,29</td>

<td> 34</td><td>Cl</td><td>H</td><td>iso-C₄H₉-</td><td>B</td><td> 80°</td><td> 5,21</td>

<td> 35</td><td>Cl</td><td>CH₃</td><td>nC₃H₇</td><td>A + B</td><td>oil</td><td> 5,00/4,81</td>

<td> 36</td><td>Cl</td><td>nC₃Hj-</td><td>C₂H_s-</td><td>R&amp;D</td><td>oil</td><td> 4,83/4,61</td>

<td> 37</td><td>Cl</td><td>H</td><td>ally allyle</td><td>A</td><td>75 ° C</td><td></td>

<td> 38</td><td>Cl</td><td>H</td><td>ally allyle</td><td>B</td><td>181 ° C</td><td></td>

<td> 39</td><td>Cl</td><td>CH</td><td>F-CH₂CH₂-</td><td>A + B</td><td>oil</td><td> 5,05/4,90</td>

<td> 40</td><td>Cl</td><td>ch₃</td><td>F-GH₂CH₂-</td><td>C + D</td><td>oil</td><td> 4,91/4,66</td>

<td> 41</td><td>Cl</td><td>ch₃</td><td>F-CH₂-CH₂-</td><td>A + B + C + D</td><td>oil</td><td> 5,05/4,91 4,90/4,66</td>

<td> 42</td><td>Cl</td><td>ch₃</td><td>cf.₃-CH₂-</td><td>A + B</td><td>oil</td><td> 5,09/4,95</td>

<td> 43</td><td>Cl</td><td>H</td><td>F-CH₂CH₂-</td><td>A</td><td> 107°</td><td> 5,29</td>

<td> 44</td><td>Cl</td><td>H</td><td>F-CH₂-CH₂-</td><td>B</td><td> 158°</td><td> 5,14</td>

<td> 45</td><td>Cl</td><td>H</td><td>c₂h₅-</td><td>A + B</td><td> . 57°</td><td> 5,30/5,14</td>

9X074

Table 1 (continued)

<td>compound Nr.</td><td>X¹</td><td>R¹</td><td>R^of</td><td>Diastereolsomers present</td><td>pt</td><td>delta (NMR)</td>

<td> 47</td><td>Cl</td><td>H</td><td>II</td><td>A + B</td><td> 171°</td><td></td>

<td> 48</td><td>Cl</td><td>nC₃II</td><td>H</td><td>A + B + C + D</td><td> 152°</td><td></td>

<td> 49</td><td>F</td><td>H</td><td>c₂h₅-</td><td>A + B</td><td>oil</td><td> 5,24 5,08</td>

<td> 50</td><td>F</td><td>H</td><td>c₂h₅-</td><td>A + B</td><td>oil</td><td> 5,24 5,12</td>

In vivo testing on Erysiphe graminis (barley) (barley oidium) plant:

It is prepared by fine spraying, an aqueous emulsion containing the active test material having the following composition: active test material 40 mg, 0.4 ml twwen 80 (surfactant consisting of an oleate of the polyoxyethylene sorbitan derivative) diluted to 10% in water and 40 ml water.

This aqueous emulsion is then diluted with water to obtain the desired concentration. Barley, in wells, sown in open ground, is treated at the stage of 10 cm height by spraying an aqueous emulsion (called boiling) of the concentration indicated above. The test is repeated twice. At the end of a period of 48 hours, the barley plants with spores of Erysiphe 'graminis are pressed, with the help of the diseased plants. The reading is performed from 8 to 12 days after contamination.

Under these conditions, the following results are observed.

A dose of one gram / ml, good or total protection with compounds: 1, 2, 4, 5, 6, 7, 8, 17, 18, 19 and 20, from table 1 below.

A dose of 0.33 g / 1 shows total protection with compounds 8, 14, 16 and 27 in Table 1.

A dose of 0.11 g / 1 shows total protection with compounds 11, 12, 13, 15 and 28 of Table 1.

A dose of 0.033 g / 1 shows total protection with compounds 9 and 10 of Table 1.

In vivo testing of Puccinia recodita, responsible for the rust rust disease.

In this case, the wheat in the wells is sown in the open ground and then treated at a height of 10 cm by spray with aqueous emulsions (called boilers) of the same composition as described above and at different concentrations of the test compound. The test is repeated 2 times with each concentration. At the end of the 48-hour period, an aqueous spore suspension (50,000 spores / cm) is sprayed over the wheat; this suspension was obtained from contaminated plants. The wheat is then brought to the incubation cell for 48 hours at a temperature of about 18 ° C and 100% relative humidity.

At the end of these two days, the relative humidity is brought to 60%. The control of the stage of the plant is done between 11 and 15 days after contamination compared to the untreated control.

Under these conditions, the following results are observed.

A dose of 1 g / 1 indicates good protection of compounds 4, 5, 6, 7, 9, 13, 14, 15, 16, 17, 18 and 21 of Table 1.

A dose of 0.33 g / 1 indicates total protection with compounds 10 and 11 of Table 1.

The test for Botrytis was fifth ₂₀ tomatoes. Tomatoes grown in greenhouses (Marmande variety) from 30 to 40 days are spray-treated with aqueous emulsions (called boilers) of the same composition as those described above and at₂₅ different concentrations of the test compound. The test is repeated 2 times with each concentration.

After 24 h, the leaves are cut and placed in 2 11 cm diameter Petri dishes,₃₀ Each bottom is pre-fitted with a wet filter paper disk (5 sheets per Petri dish).

The inoculation is then performed with the aid of a syringe by depositing the drops of a ₃₅ spore suspensions (3 drops on each leaf). This suspension containing the spores of Botrytis was obtained from a culture of 15 days, but then this suspension is brought to a solution₄₀ nutritious (800 000 units / cm³).

The control is carried out 3 days after contamination, in comparison with the untreated control.

under these conditions, at the dose of ₄5 1 g / 1 good protection or total protection with compounds number 8, 10 and 16 of table 1.

In vitro test carried out with seed fungi and soil fungi.

The action of the compounds according to the present invention is studied on the following types of fungi responsible for the secondary diseases of cereals: Cercosporella herpotrichoides (CERC), Helminthosporium gramineum (HELM G), Pyrenophorae avenae (PYRE), Septoria nodorum (SEPT), Helptorium (SEPT) ) Fusarium roseum (FUS ROS), Fusarium nivale (FUS NIV), Fusarium culmorum (FUS CULM) and Rhizoctonia cerealis (RHIZ C).

The information in brackets will be used to represent the mushrooms in table number 2.

For each test, it is operated as follows: a nutrient medium consisting of potatoes, glucose and jelly (PDA medium) is introduced by overfilling in a series of Petri dishes after sterilization in autoclaves at a temperature of 120 ° C.

During the filling of these boxes, an acetonic solution containing the active raw material is injected into the respective medium, to obtain the desired final concentration.

We take as a series of Petri dishes similar to the previous ones, in which similar quantities are obtained from the nutritional environment that does not contain the active substance.

After a period of 24 or 48 hours, each Petri dish is seeded by depositing a mycelium fragment from a previous culture containing the same type of mushrooms.

These boxes are then stored for two to ten days (only the mushrooms tested) at a temperature of 22 ° C and then the growth of the mushrooms in these boxes is compared, containing the active test material, with the one containing the same mushroom in the box used as control.

It is thus determined for each tested composition, the lowest dose that allows the inhibition of 80 to 100% of the growth of the considered mushroom. This dose is called the "minimum inhibition dose".

These minimum doses of inhibition, expressed in parts per million, are reported in table 2, where the abbreviations have the meanings indicated above.

The compounds according to the present invention can therefore be used in both preventive and curative control against fungi, especially fungi of the type of basidomieets, ascomycetes, adelomycetes or imperfect fungi, especially those that cause rust, oidium, bedtime. plants, fusariosis, helminthosporiosis, septoriosis, rhizoctomies of plants and plants in general and in particular in cereals such as gray, barley, rye, wild oats and hybrids of these cereals and also rice and corn.

The products according to the present invention are, in particular, interesting because of their broad spectrum in cereal diseases (oidium, rust, cereal bedding, helminthosporosis, septeriosis and especially fusariosis difficult to control). They are also of great interest depending on the activity of the cirrhospores and for this reason they can be applied on quite varied crops of vines, on crop crops and in arboriculture.

Finally, these compounds exhibit excellent selectivity to cultures.

These compounds can be advantageously applied in doses ranging from 0.02 to 5 kg / ha, preferably from 0.05 and more preferably from 0.1 to 2 kg / ha.

For their practical use, the compounds of the present invention are rarely used as such. Most often they are part of compositions. These compositions, usable for the protection of plants against fungicidal diseases or in plant growth control compositions, containing as active substance a compound according to the present invention, as mentioned above, in association with acceptable supports in agriculture and surfactants in a manner. equally acceptable in agriculture. in particular, the inert and usual carrier substances and the usual surfactants are usable.

These compositions may also contain any type of ingredient, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestrants, etc., as well as other active materials with properties. pesticides (in particular, insecticides or fungicides) with plant growth promoting properties (in particular, fertilizers) or with plant growth control properties. Generally, the compounds according to the present invention can be associated with any additive substance, which corresponds to the usual techniques for converting them to formulas.

These dosages of use in the case of fungicide use of the compounds of the present invention may vary to a large extent, especially depending on the virulence of the fungi and depending on the climatic conditions.

Generally speaking, compositions containing from 0.5 to 5,000 ppm of active substance are the most convenient; these values ​​are indicated for compositions prepared for application. By parts per million is meant the weighted percentage abbreviated by ppm. The area from 0.5 to 5,000 ppm corresponds to an area of ​​5 x 10 ~⁵ up to 0.5% (weight percentages).

In terms of compositions adapted to storage or transport, they contain the most advantageous from 0.5 to 95% by weight of the active substance.

Thus, the compositions used in agriculture according to the present invention, may contain the active substances according to the present invention within very wide limits, ranging from 5 · 10 '⁵ up to ninety-five percent by weight.

According to the aforementioned, the compounds of the present invention are generally associated with supportive substances and possibly with surfactants.

By the term "support substance" is meant herein any organic or mineral matter, natural or synthetic, with. which raw material can be easily associated for application on plants, seeds or soil. These supporting substances are generally inert and they must be acceptable in agriculture, in particular on treated plants. These support substances are liquid substances such as water. alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gas, etc.

The surfactant may be an ionizing, dispersing or wetting agent, or a nonionic type. Examples include polyacrylic acid salts, lignosulphonic acid salts, phenolsulfonic or naflalensulphonic acid salts polycondensated ethylene oxide compounds with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkyl phenols). taurine (especially acetylation), salts of sulfosuccinic acid esters, derivatives of phosphoric esters of polyoxyethylated alcohols or phenols. The presence of less than one surfactant is generally indispensable when the raw material and / or the inert carrier are not water soluble and when the vector of application agent is water.

For their application, the compounds of formula Γ are thus generally found in the form of compositions; these compositions according to the present invention are themselves in quite different form.

As forms of liquid compositions or intended to constitute liquid compositions when applied, solutions, especially water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, for application containing from 0.01 to 20% in the active substance can be cited. In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of close additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes, active substances. By way of example, the composition of such concentrates is given.

Other examples have also been made in Table 2, in which the following abbreviations are used: Botrytis cinerea BOT, Erysiphe graminis ERYG, Puccinia reconcilia PUCR, Plasmopora viticola PLA, Piricularia oryzae PIR, Cercospora beticola ORET, Peronospora tabacin PERO, Poninia succin , Erysiphccichoracearum ERYC, Fusarium oxysporum (melons) FUSOX. Pgthium species PYT, Pyrenophora avenae PYR, Seploria irit here SEPT T, Venluria inec / nalis VENT, Whelzelinia scleroliorum WLIE, Monilia laxa MON, Mycosphaerella fijiensis MSPH, Martanina panaUoniana MARȘ, Alternation solani ALT, Aspcridacea, ASpcrgorum Aphracillus, Arpyridaceae, ASPcrgorum Cercar herbarum CLAD, Helminihosporium oryzae HELM OR, Periciltium expancum PEN, Pestalozzia species PES, Phialophora cinerescens PITI, Phoma belac PHB, Phoma j'oveala PHR, Phoma lingam PIIL, Ustilago maydis IJST, Vcrlicillium daliae VERT, Ancockyra pişi ASC.Q, Guiynardia bidiveUii G, Corlicium rolfsii ORO, Phomopsis viticola PIIY, Sclatinia sclcroliorum SCL S, Sclerolinia minor SCL M, Phyaplhora cinnamomi PITA⁷ CI, Phytophlhora caclorum PIIY C, Phytophthora capsisi PIIY CP, Phylophthora infestans P, Phytophthora parasiiica PIIY PA, Phytophthora megasperas PHY M, Phytophlora ayrinqac PITA⁷ SY, Corynenm cardinale CORY, 'Rhyzodonia solani RHIZ S.

The sign> is greater than, and the sign <means less than or equal to.

With regard to the bed-bug disease of plants, it is produced in the highest degree by the fungus CercosporclFi herpolrichoidcs, but this fungus is commonly called Pscin'ocerospor sila herpolrichoides.

Tables. 3, 4 and 6 show the minimum in vitro inhibition doses of the different compounds, with respect to the different fungi according to the application method used above.

Table number 5 presents the minimum inhibition dose in the greenhouse (in vivo) of different compounds with respect to different fungi according to the application methods used above.

Table number 7 shows the efficiency of the products in full field compared to different compounds.

Leave to incubate for 72 hours at 25 ° C and in 100% humidity conditions, then after three days. seedlings (shoots) are placed under the light of 10,000 lux, for about 14 hours a day. The control of the stage of these shoots is carried out 14 days after the contamination and is expressed as a percentage in relation to an untreated control. An effect identical to the control is noted with 0% ·

The special conditions of the different tests are indicated in table number 7. The general conditions are as follows: the tests

Table 2

Minimum doses of inhibition in ppm

<td>com- Pusula Ed.</td><td>CIRCLE</td><td>HELM G</td><td>pyre</td><td>HELM T</td><td>SEPT N</td><td>FUS ROS</td><td>FUSE XIV</td><td>FUS CULM</td><td>RHIZ C</td>

<td> 1</td><td></td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td></td><td></td><td> 100</td><td></td>

<td> 2</td><td></td><td> 33</td><td></td><td></td><td> 33</td><td></td><td></td><td> 33</td><td></td>

<td> 3</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 4</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 33</td><td> 33</td><td> 100</td>

<td> 5</td><td> 100</td><td></td><td></td><td></td><td></td><td></td><td> 100</td><td> 100</td><td> 100</td>

<td> 6</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 33</td><td> 33</td><td> ...... 100</td>

<td> 7</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 33</td><td> 33</td><td> 100</td>

<td>⁸</td><td> 11</td><td> 100</td><td></td><td></td><td></td><td> 33</td><td> 33</td><td> 33</td><td> 100</td>

<td> — 9</td><td> 1,1</td><td> 11</td><td> 3,3</td><td> 3,3</td><td> 3,3</td><td> 33</td><td> 33</td><td> 11</td><td> 11</td>

<td> 10</td><td> 3,3</td><td> 11</td><td> 3,3</td><td> 1,1</td><td> 1,1</td><td> 11</td><td> 11</td><td> 11</td><td>^u 1</td>

<td> 11</td><td> 3,3</td><td> 100</td><td> 33</td><td> 33</td><td> 1,1</td><td> 100</td><td> 100</td><td> 33</td><td>33 days</td>

<td> 12</td><td> 1,1</td><td> 33</td><td> 11</td><td> 1,1</td><td> 3,3</td><td> 33</td><td> 33</td><td> 33</td><td> 11</td>

<td> 15</td><td> 100</td><td> 33</td><td> 33</td><td> 33</td><td> 33</td><td> 100</td><td> 100</td><td> 33</td><td> 33</td>

<td> 16</td><td> 11</td><td></td><td></td><td></td><td> 100</td><td> 33</td><td> 33</td><td> 33</td><td>100 i</td>

<td> 17</td><td> 1,1</td><td></td><td> 11</td><td> 3,3</td><td> 3,3</td><td> 33</td><td> 33</td><td> 33</td><td> 11</td>

<td> 18</td><td> 3,3</td><td></td><td> 33</td><td> 33</td><td> 33</td><td> 33</td><td> 33</td><td> 33</td><td> 11</td>

<td> 19</td><td> 3,3</td><td></td><td> 11</td><td> 11</td><td> 11</td><td> 33</td><td> 33</td><td> 33</td><td> 11</td>

<td> 20</td><td> 1,1</td><td> 100</td><td> 33</td><td> 33</td><td> 100</td><td> 33</td><td> 100</td><td> 33</td><td> 11</td>

<td> 21</td><td> 100</td><td> 11</td><td> 1.1</td><td> 11</td><td> 11</td><td> 100</td><td> 100</td><td> 100</td><td> 33</td>

<td> 22</td><td> 110</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

<td> 25</td><td></td><td> 100</td><td> 100</td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

Minimum doses of inhibition in ppm

<td>Mushroom</td><td>compound no.</td><td>Minimum dose of inhibition</td>

<td>OTHER</td><td> 29</td><td> 30</td>

<td>ASP</td><td> 29</td><td> 100</td>

<td>BOT</td><td> 29</td><td> 10</td>

<td>GARA</td><td> 29</td><td> 100</td>

<td>GARA</td><td> 29</td><td> 3</td>

<td>CLAD</td><td> 29</td><td> 30</td>

<td>FUS CULM</td><td> 29</td><td> 30</td>

<td>FUS OX</td><td> 29</td><td> 100</td>

<td>HELM OR</td><td> 29</td><td> 100</td>

<td>PEN</td><td> 29</td><td> 100</td>

Table 3

<td>Mushroom</td><td>compound no.</td><td>Minimal inhibition dance</td>

<td>PES</td><td> 29</td><td> 30</td>

<td>PHI</td><td> 29</td><td> 30</td>

<td>j PHB</td><td> 29</td><td> 10</td>

<td>PHF</td><td> 29</td><td> 100</td>

<td>PHL</td><td> 29</td><td> 10</td>

<td>PHY CI</td><td> 29</td><td> 100</td>

<td>PHY CC</td><td> 29</td><td> 100</td>

<td>PHY CP</td><td> 29</td><td> 100</td>

<td>PHY IN</td><td> 29</td><td> 100</td>

<td>PHY NOT</td><td> 29</td><td> 100</td>

<td>PHY ME</td><td> 29</td><td> 100</td>

<td>PHY SY</td><td> 29</td><td> 100</td>

Table 3 (continued)

<td>Mushroom</td><td>Gnmpusul no.</td><td>Minimum dose of inhibition</td><td rowspan="17"></td><td>Mushroom</td><td>compound no.</td><td>Minimum dose of inhibition</td>

<td>SCL S</td><td> 29</td><td> 10</td><td>WI-IE</td><td> 29</td><td> 10</td>

<td>UST</td><td> 29</td><td> 3</td><td rowspan="5">PIR</td><td> 31</td><td> 30</td>

<td>VERT</td><td> 29</td><td> 10</td><td> 28</td><td> 10</td>

<td rowspan="2">ASCO</td><td rowspan="2"> 29</td><td rowspan="2"> 30</td><td> 35</td><td> 10</td>

<td rowspan="2"> 28</td><td rowspan="2"> 10</td>

<td rowspan="2">Guigui</td><td rowspan="2"> 29</td><td rowspan="2"> 100</td>

<td rowspan="3">MON</td><td> 29</td><td> 10</td>

<td>CRO</td><td> 29</td><td> 10</td><td> 35</td><td> 30</td>

<td>SEPT T</td><td> 29</td><td> 100</td><td> 31</td><td> 10</td>

<td>PHV</td><td> 29</td><td> 30</td><td rowspan="4">MSPH</td><td> 28</td><td> 10</td>

<td>SCL M</td><td> 29</td><td> 10</td><td> 29</td><td> 1</td>

<td>CORY</td><td> 29</td><td> 30</td><td> 35</td><td> 10</td>

<td rowspan="4">VENT</td><td> 31</td><td> 10</td><td> 28</td><td> 30</td>

<td> 28</td><td> 3</td><td rowspan="3">MARCH</td><td> 29</td><td> 1</td>

<td> 29</td><td> 3</td><td> 28</td><td> 10</td>

<td> 35</td><td> 10</td><td> 29</td><td> 10</td>

Table 4

<td rowspan="2">Compound no.</td><td></td><td></td><td></td><td colspan="4">Minimum inhibition dose in ppm</td><td></td><td></td><td></td>

<td> 28</td><td> 29</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td><td> 34</td><td> 35</td><td> 36</td><td> 37</td>

<td>BUT</td><td> 10</td><td> 10</td><td> 30</td><td> 100</td><td></td><td></td><td></td><td> 10</td><td></td><td> 10</td>

<td>FUS OX</td><td> 100</td><td> 100</td><td> 100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td>

<td>Pyi</td><td> 100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> 100</td><td> 100</td><td></td><td> &gt;100</td><td> &gt;100</td>

<td>RHIZ S</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 30</td><td> 30</td><td> 100</td><td> 30</td><td> 100</td><td> 3</td>

<td>FUS CULM</td><td> 30</td><td> 30</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 30</td><td> 100</td><td> 100</td>

<td>FUS NIV</td><td> 30</td><td> 30</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

<td>FUS ROS</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 30</td><td> 30</td><td> 100</td>

<td>CIRCLE</td><td> 10</td><td> &lt;1</td><td> 10</td><td> 100</td><td> 30</td><td> 30</td><td> 100</td><td> 10</td><td> 30</td><td> 10</td>

<td>HELM G</td><td> 10</td><td> 3</td><td> 10</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 10</td><td> 100</td><td> 30</td>

<td>pyre</td><td> 10</td><td> 10</td><td> 10</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td>

<td>HELM T</td><td> 3</td><td> 3</td><td> 3</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td>

<td>SEPT N</td><td> 3</td><td></td><td> 3</td><td> 30</td><td> 100</td><td> 30</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td>

<td>RITIZ C</td><td> 30</td><td> &lt;1</td><td> 10</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 10</td><td> 10</td><td> 100</td>

<td>SEPT T</td><td> &gt;100</td><td></td><td> 100</td><td> &gt;100</td><td></td><td> &gt;100</td><td></td><td></td><td></td><td> 100</td>

Table 4 (continued)

<td>Mushroom</td><td colspan="2">38 j 39</td><td> 40</td><td> 41</td><td> 42</td><td> 43</td><td> 44</td><td>⁴⁹</td><td> 50</td>

<td>BOT</td><td></td><td> 10</td><td></td><td> 10</td><td> 30</td><td> 30</td><td></td><td> 100</td><td> 100</td>

<td>FUS OX</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td> &gt;100</td><td></td><td></td><td></td><td></td>

<td>PYT</td><td> &gt;100</td><td></td><td> &gt;100</td><td></td><td></td><td> &gt;100</td><td></td><td></td><td></td>

<td>RHIZ S</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td></td><td></td><td> 100</td>

<td>FUS CULM</td><td> 100</td><td> 30</td><td> 100</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

Table 1 (continued)

<td>compound</td><td></td><td></td><td colspan="5">Minimum dose of inhibition in pmp</td><td></td><td></td>

<td>Nr.</td><td> 51</td><td> 52</td><td> 53</td><td> 54</td><td> 55</td><td> 56 |</td><td> 57</td><td> 58</td><td> 59</td>

<td>FUS NIV</td><td> 100</td><td> 30</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> &gt;100</td><td> 100</td><td> 100</td>

<td>FUS ROS</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td></td><td> &gt;100</td><td> 100</td>

<td>CIRCLE</td><td> 10</td><td> 10</td><td> 100</td><td> 10</td><td> 100</td><td> 3</td><td> 100</td><td> 10</td><td> 10</td>

<td>FIELM G</td><td> 100</td><td> 100</td><td> 100</td><td> 30</td><td> 100</td><td> 30</td><td> &gt;100</td><td> 100</td><td> 100</td>

<td>pyre</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td><td> 10</td><td> 30</td><td> &gt;100</td><td> 100</td><td> 10</td>

<td>HELM T</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td><td> 10</td><td> 30</td><td> 100</td><td> 30</td><td> 10</td>

<td>SEPT N</td><td> 100</td><td> 10</td><td> 100</td><td> 10</td><td> 10</td><td> 10</td><td> 100</td><td> 30</td><td> 30</td>

<td>RHIZ C</td><td> 100</td><td> 30</td><td> 100</td><td> 30</td><td> 30</td><td> 100</td><td> &gt;100</td><td> 100</td><td> 100</td>

<td>SEPT T</td><td> 100</td><td></td><td></td><td></td><td></td><td> &gt;100</td><td> &gt;100</td><td></td><td></td>

Table 5

<td>Mushroom</td><td colspan="3"> 28 | 29 | 30</td><td> 31</td><td> 32</td><td> 33</td><td> 34</td><td colspan="2"> 35 | 36</td><td> 37</td>

<td>BOT</td><td> 1000</td><td> 330</td><td></td><td></td><td></td><td></td><td></td><td> 1000</td><td></td><td> 1000</td>

<td>ERYG</td><td> 110</td><td> 110</td><td> 110</td><td> 330</td><td> 110</td><td> 110</td><td> 330</td><td> 110</td><td> 110</td><td> 1000</td>

<td>PUCR</td><td> 110</td><td> 110</td><td> 110</td><td> 330</td><td> 110</td><td> 110</td><td> &gt;1000</td><td> 110</td><td> &gt;1000</td><td> 1000</td>

<td>PLA</td><td> 100</td><td></td><td></td><td rowspan="2"> 1000 1000</td><td> 330</td><td> 1000</td><td> 1000</td><td> &gt;1000</td><td> &gt;1000</td><td> &gt;1000</td>

<td>PIR</td><td> 1000</td><td> 1000</td><td></td><td></td><td> &gt;1000</td><td></td><td> 110</td><td> 1000</td><td></td>

<td>cbet</td><td> 1000</td><td> 110</td><td></td><td> 1000</td><td> 330</td><td> 1000</td><td> 1000</td><td> 330</td><td> 1000</td><td> 1000</td>

<td>PUCS</td><td>250</td><td>îj250</td><td> ^250</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Eryc</td><td> 125</td><td> 125</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

Table 5 (continued)

<td rowspan="2">Compound no Mushroom</td><td colspan="9">Minimum inhibition dose in ppm</td>

<td> 38</td><td> 39</td><td> 40</td><td> 41</td><td> 42</td><td> 43</td><td> 44</td><td> 49</td><td> 50</td>

<td>BUT</td><td></td><td> &gt;1000</td><td></td><td></td><td> &gt;1000</td><td> 1000</td><td></td><td> 1000</td><td></td>

<td>ERYG</td><td> 1000</td><td> 330</td><td> 1000</td><td> 1000</td><td> 110</td><td> 330</td><td> &gt;1000</td><td> 330</td><td> 1000</td>

<td>PUCR</td><td></td><td> 1000</td><td> &gt;1000</td><td> 1000</td><td> 1000</td><td> 1000</td><td></td><td> &gt;1000</td><td> &gt;1000</td>

<td>PLA</td><td></td><td> &gt;1000</td><td> &gt;1000</td><td></td><td> &gt;1000</td><td></td><td></td><td></td><td> &gt;1000</td>

<td>PIR</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>cbet</td><td> &gt;1000</td><td> 330</td><td> 1000</td><td> 330</td><td> 330</td><td> 330</td><td> 1000</td><td> &gt;1000</td><td></td>

<td>PUCS</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Eryc</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

Table 6

<td rowspan="2">Compound no. Mushroom</td><td colspan="8">Minimum inhibition dose in ppm.</td>

<td> 45</td><td> 29 ]</td><td> 12 )</td><td> 35</td><td> 9</td><td> 28</td><td> 47</td><td> 48</td>

<td>BOT</td><td> 30</td><td> 10</td><td> 100</td><td> 10</td><td> 30</td><td> 10</td><td> 100 (0)</td><td> 100</td>

<td>FUS CULM</td><td> 100</td><td> 30</td><td> 100</td><td> 30</td><td> 11</td><td> 30</td><td> 100</td><td> &gt;100 (80)</td>

<td>FUS NIV</td><td> 100</td><td> 30</td><td> 100</td><td> 100</td><td> 33</td><td> 30</td><td> &gt;100</td><td> 30</td>

<td>FUS ROS</td><td> 100</td><td> 100</td><td> &gt;100</td><td> 30</td><td> 33</td><td> 30</td><td> &gt;100 (80)</td><td> &gt;100 (50)</td>

<td>CIRCLE</td><td> 30</td><td>= Sl</td><td> 30</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>HELM G</td><td> 30</td><td> 10</td><td> 100</td><td> 10</td><td> 11</td><td> 10</td><td> &gt;100</td><td> 30</td>

<td>pyre</td><td> 10</td><td> 3</td><td> 30</td><td> 10</td><td> 3,3</td><td> 10</td><td> &gt;100</td><td> 30</td>

<td>HELM T</td><td> 3</td><td> 3</td><td> 10</td><td> 10</td><td> 3,3</td><td> 3</td><td> 100</td><td> 10</td>

<td>SEPT N</td><td> 3</td><td> &lt;1</td><td> 30</td><td> 10</td><td> 3,3</td><td> 3</td><td> 100</td><td> 10</td>

<td>RHIZ C i</td><td> 10</td><td> &lt;1</td><td> 30</td><td>io</td><td> 11</td><td> 30</td><td> &gt;100</td><td> 30</td>

The figures in parentheses indicate the degree of hibernation in percentages at the mentioned dose.

Table 7

<td>Mushroom</td><td>Compound no</td><td>Dosage g / ha</td><td>Percentage of plants ill</td><td>Percentage of leaves ill</td><td>Ways of observing 1 results</td>

<td>PUCS</td><td>witness</td><td> 0</td><td></td><td> 40</td><td>23 days after treatment; observe</td>

<td></td><td></td><td> 250</td><td></td><td> 17,5</td><td>varca of the whole diseased plant</td>

<td></td><td> 45</td><td> 500</td><td></td><td> 16,3</td><td>in stage 4 of the defeat (</td>

<td></td><td></td><td> 250</td><td></td><td> 7,9</td><td></td>

<td>PUCS</td><td>witness</td><td> 0</td><td></td><td> 82,3</td><td>14 days after treatment; ob- |</td>

<td></td><td> 45</td><td> 125</td><td></td><td> 3,4</td><td>serving on the leaf 3.</td>

<td></td><td> 29</td><td> 125</td><td></td><td> 1,2</td><td></td>

<td>PUCS</td><td>witness</td><td> 0</td><td></td><td> 25,9</td><td>15 days after treatment,</td>

<td></td><td> 45</td><td> 125</td><td></td><td> 6,7</td><td>leaf observation 1</td>

<td></td><td> 29</td><td> 125</td><td></td><td> 3,5</td><td></td>

<td>ERYG</td><td>witness</td><td> 0</td><td></td><td> 25,9</td><td>14 days after treatment; ob-</td>

<td></td><td> 45</td><td></td><td></td><td> 4,7</td><td></td>

<td></td><td> 29</td><td> 250</td><td></td><td> 1,0</td><td>serving on the leaf 3</td>

<td>PUCS</td><td>witness</td><td> 0</td><td> 100</td><td rowspan="2"> 47,7 5,8</td><td>22 days after the second treatment-</td>

<td></td><td> 12</td><td> 125</td><td> 88</td><td>mind of the plant; 7 days later</td>

<td></td><td> 28</td><td> 125</td><td> 64</td><td> 0,8</td><td>the second treatment. leaf control.</td>

<td>ERYG</td><td>witness</td><td> 0</td><td></td><td> 10,3</td><td>20 days after the second treatment.</td>

<td></td><td> 12</td><td> 125</td><td></td><td> 0,9</td><td>control at the first leaf.</td>

<td></td><td> 28</td><td> 125</td><td></td><td> 0,1</td><td></td>

<td>PUCS</td><td>witness</td><td> 0</td><td> 96</td><td></td><td>24 days after treatment.</td>

<td></td><td> 45</td><td> 125</td><td> 74</td><td></td><td></td>

<td></td><td></td><td> 250</td><td> 74</td><td></td><td></td>

<td></td><td> 29</td><td> 125</td><td> 54</td><td></td><td></td>

<td></td><td></td><td> 250</td><td> 46</td><td></td><td></td>

<td></td><td> 12</td><td> 125</td><td> 91</td><td></td><td></td>

<td></td><td></td><td> 250</td><td> 87</td><td></td><td></td>

<td></td><td> 28</td><td> 125</td><td> 39</td><td></td><td></td>

<td></td><td></td><td> 250</td><td> 46</td><td></td><td></td>

<td colspan="6">percent of diseased stem</td>

<td>CERO</td><td>witness</td><td> 0</td><td> 93</td><td></td><td></td>

<td></td><td> 45</td><td> 500</td><td> 96</td><td></td><td></td>

<td></td><td></td><td> 1000</td><td> 90</td><td></td><td></td>

<td></td><td> 29</td><td> 500</td><td> 82</td><td></td><td></td>

<td></td><td></td><td> 1000</td><td> 72</td><td></td><td>56 days after treatment:</td>

<td></td><td> 12</td><td> 500</td><td> 93</td><td></td><td>control on the main stem.</td>

<td></td><td></td><td> 1000</td><td> 85</td><td></td><td></td>

<td></td><td> 28</td><td> 500</td><td> 82</td><td></td><td></td>

<td></td><td></td><td> 1000</td><td> 63</td><td></td><td></td>

AND they are repeated four times each, on plots of land from 3 to 5 m². Contamination is natural for the Oidium (ERYG), artificial for the CERC fungus which leads to the laying of plants on the ground and also the yellow rust rust (PUCR). The plants were treated with a mixture spread on the order of 500 up to 1000 1 / ha under pressure of. 3 kg / cnr².

The treatment was preventive for oidium and for yellow rust (the treatment is repeated for 15 days), curative for laying the plant · on the ground. The results were observed by taking 25 leaves for powdery mildew and for yellow rust (determining the percentage for the surface of the leaves affected by the disease) or by taking the rods for the grounding of the plants (determining the percentage of the rods affected by the disease).

Other explanations besides those described above: the products according to the present invention have an excellent biocidal activity with respect to Ja numerous other varieties of microorganisms among which sc can be mentioned without limitation, the mushrooms belonging to the following genera: Piilliilaria, with the species P. Pullulans, Chacloiniuin species C. Globosum, Asper (jilJnx with species Aspergillus niger, Conophora and species C. Puleana.

As a result of their biocidal activity, the products according to the present invention allow to combat the effectiveness of microorganisms whose proliferation creates numerous problems in the agricultural and industrial fields. For these reasons, these compounds are very well suited to the protection of plants or industrial products such as wood, leather, paints, paper, cane, plastics, circuits and industrial water. These compounds are especially suited to the protection of lignocellulosic products and especially for wood protection, when it comes to wood for furniture making, timber for construction exposed to the weather, as well as wood for the fence, cutters for vines and sleepers for the road. rail.

In the compositions according to the present invention, the products used in the treatment of wood may possibly be associated with one or more biocidal products known as pentachlorphenol, metal salts, in particular copper, magnesium, cobalt, chromium, zinc, mineral acid derivatives. carboxylic acid (heptanoic, ictanoic acids, naphthenic acid), organic complexes of ethane and mercaptobenzothiazole.

The biocidal activity of the compounds according to the present invention is further illustrated.

A microsuspension of the product is prepared to determine its fungal properties. This microsuspension is prepared in the following manner: In a ball-homogenizing apparatus, a ml of aqueous solution containing two wetting agents containing 4% polyglycol 400 and 0.4% is obtained by means of a tube. of Tween 80, then 5 g of mm diameter glass balls and 3 g of 5 mm diameter glass balls. The mixture from the apparatus is stirred until the mixture becomes of the consistency of a homogeneous microsuspension.

Quantities thus determinant of microsuspension are introduced into a culture medium containing jelly in hemolysis tubes. Each of these environments is sown with a strain determined by the fungus. For each crop, the amount of biocidal product is varied. The active fungicidal dose is expressed by the amount of biocidal product per 100 ml of the culture medium used, and at this dose, the influence of the product on the development of the respective layer is noted.

The mixtures were classified into five categories of increasing functional efficacy.

Class: zero, total inefficiency at value 1.10^-2; zero plus with neighboring efficiency with value 1.10^-2; Ineffectiveness between and 1.10 "³; Neighboring inefficiency with value of 1.10 "³; 2 ^ the efficiency between the values ​​1.10³ and 1.10 2⁺ = efficiency between 1.10 "⁴; 3 = efficiency between 1.10⁴ and 1.10⁵; 3⁺ = efficiency in the vicinity of the value of 1.10⁵;

== the effectiveness between 1.10⁵ and 1.10⁸; 44 '^ efficiency of 1.10^-e and 5 == the effectiveness between 1.10^G and 1.10⁷.

The fungicidal doses of these mixtures are determined for the following strains: Goriolus versicolor; Coniophora puteana, Pul lularia pullulans, Cbaetomium globosum and Sterrigmatocystis nigra (Aspergillus niger).

The results obtained are recorded in the following table and are given in comparison with those obtained under the same experimental conditions with pcntachlorphenol.

<td>Fugitive activity on</td><td>Efficacy doses The compound no. 28</td><td>(Classes) Pentacle phenol</td>

<td>Coriolus versicolor</td><td> 4</td><td> 3</td>

<td>Coniophora puteana</td><td> 4 +</td><td> 3</td>

<td>Gyrus pullulans</td><td> 4</td><td> 3</td>

<td>Chaetoinium globosum</td><td> 3</td><td> 3</td>

<td>Aspergillus niger</td><td> 2 +</td><td> 3</td>

The products according to the present invention are especially advantageous for the treatment of wood.

The compounds according to the invention can be obtained by treating compounds of general formula II:

(Χ) „ο

Q- / χ⁰*²

-Ri (Π) ch₂z wherein Z is a chlorine atom or a bromine atom and X, n, R_x and R₂ have the same meaning as in formula I, with an alkaline derivative, for example a sodium salt or a potassium salt or a quaternary ammonium or phosphonium derivative of an imidazolid compound or a triazolic compound.

The reaction is typically carried out in an aprotic polar solvent and can also be catalyzed, for example, by the addition of alkaline iodide, at a temperature generally between 50 and 250 ° C, preferably between 70 and 230 ° C. For economic reasons, the global concentrations in the reagent are between one and 50%, these concentrations being used most frequently.

Compounds of the following formula:

the aid of acetyl chloride which reacts with the alcohol present in the reaction to give rise to hydrochloric acid. This reaction is usually carried out by simply heating the indicated reagents. The reaction temperature is generally within the temperature range from 50 ° C to the boiling temperature of the reaction medium. Alcohol of general formula

R₂0H usually plays the role of solvent in the reaction medium. An inert cosolvent may also be added to the reaction medium, in particular an aliphatic, allylic or aromatic hydrocarbon, halogenated or non-halogenated or a steric compound. Compounds of formula III are typically prepared by reacting a carbonylated compound of general formula III a:

Z ~~ \ -CO-CH₂ Z (lilac)

OR₂ (X) »/⁺v / ° \ _

-Ri (Ha) ch₂z can be prepared by the reaction between an alcohol of the following formula:

X „OH Rj OR₃

<img file="RO91074A_D0002.tif" />

<img file="RO91074A_D0003.tif" />

ch₂z in the presence of an acid catalyst, radicals¹Ri, R₂, X, Z and n being of the same meaning as before, and the radical R₃ being an organic radical, preferably a lower alkyl, having from one to four carbon atoms, two radicals R₃ being able to form together a bivalent organic radical, preferably a lower alkylene.

The acid catalyst employed in this reaction can be a protic or aprotic acid. As protic acids, for example hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloric acid, benzene-sulfonic acid, toluene-sulfonic acid and methane-sulfonic acid. Lewis acids, such as trifluoride boron, BF, can be cited as aprotic acids.₃, A1C1 aluminum trichloride₃ and SnCl tin tetrachloride₄. When hydrochloric acid is used as a catalyst, tin tetrachloride can be generated in situ, for example with the acyl chloride oxide and in particular with an organomagnetic derivative prepared.³⁵ starting from a compound of the general formula Illb:

R_x OR₃I i

Z'— CH, —CH — CH ..... OR, (Illb), ^{2 3} wherein Z is a halogen atom, preferably bromine, and X, Z, R_x, R₃ and n have the same meaning indicated above. The organomagnesian derivative can be prepared in a manner known in the art, by the action of a catalytic compound of iota-halogenoaldehyde on magnesium in solvent medium. This ketalic compound of Zie / a-halogenaldehyde can₄₀ himself to be prepared according to methods known in the literature. The reaction between the compound of formula Ha and the organomagnesian derivative of the compound of formula Illb, is performed₄₅ most often at a temperature between minus 70 ° C and + 100 ° C, preferably between -50 ° C and + 50 ° C. The solvent used in the reaction may be mentioned the group of ethers, in particular diethyl ether and tetrahydrofuran or aliphatic, alicyclic or aromatic hydrocarbons, as well as the mixture of these hydrocarbons.

According to another preparation process, the compounds according to the present invention may ₅₅ be obtained by the reaction between an alcohol with

<td>formula formula</td><td>General R₂0H General IV:</td><td>with the compound with</td>

<td>(X) "</td><td>OH Rj</td><td>or₃</td>

<td>is</td><td>1 1 —C-CH, -CH₂-</td><td>1 CH-OR₃</td>

<td> \₌x</td><td>and CIT₂ -N-W</td><td>(IV)</td>

in the presence of an acid catalyst. The different symbols indicated for the formulas of the two reagents have the same meaning given above. As the acid catalyst, the group of compounds of formula Ila may also be used. The other reaction conditions are also similar to those defined for the preparation of compounds of formula Ila. Compounds of general formula IV can be obtained by reaction between the imidazole compound or the triazole compound with the compound of the general formula λ⁷:

(X) n

X-CC — CH —— CH — CH — OR, (V)

RI OR, reaction at -45 ° C and a solution of 56.7 g (0.3 mol) of chloromethyl- (parachlorophenyl)-ketone in 150 ml of tetrahydrofuran is added, the temperature being kept at this time at value of -45 ° C. After a time of 30 minutes, the reaction medium is neutralized with a volume of 120 ml of pure acetic acid, and then brought to a liter of water. An extraction operation is carried out using ethyl acetate. The solution obtained in ethyl acetate is dried and evaporated. In this way an amount of 100 g of hydrochloride is melted which melts at 99 ° C (after recrystallization from cyclohexane), having the following formula:

OH where the different symbols have the same meaning as the ones mentioned above. ²⁰

The imidazole compound or the triazole compound may be wholly or preferably partially in the form of an alkali salt. The reaction is usually carried out at a temperature between²⁵which is 20 ° C and between boiling temperature at reflux, this temperature preferably being between + 50 ° C and + 130 ° C. As solvents, especially alcohols, ethers and solvents may be used³⁰aprotic polar, such as dimethylformamide and dimethylsulfoxide.

Under conditions similar to those commonly used in the preparation of compounds of formula IV, starting from the compounds of formula V, these compounds of formula IV can also be prepared, departing from the compounds of formula III and with the aid of the imidazole alkaline derivative. or triazole. Compounds of formula V can be obtained by dehydrohalogenation of compounds of formula III. This reaction is usually carried out by the action of an organic base or preferably by the action of a mineral base, at a temperature between 0 ° C and 100 ° C. The reaction medium may be aqueous and / or may contain a solvent such as, for example, a hydrocarbon or an ether, an alcohol, a polar solvent.

The following are some methods for preparing the compounds according to the invention.

A. Prepare an organomagnesian derivative by activating a quantity of dc 9.7 g of magnesium (0.4 mol) with 0.5 ml of dibromethane and 10 ml of anhydrous tetrahydrofuran (THF), maintaining the mixture at a lower temperature. reaction at 15 ° C, adding dropwise a solution of 47 ml (0.4 mol) of 6e / a-bromethyl-2-dioxolan-1,3 in 200 ml of tetrahydrofuran. At one quarter of an hour after the addition is complete, the mixture of p c -C is cooled₆H₄ -C-CH, -CH₂ —CH — O —CH₂

III

CH₂C1 or --- ch₂ (VI)

Heat for 2 hours at boiling temperature at reflux, a mixture of 0.1 ml of acetyl chloride and a solution of 6 g (0.02 mol) of the product of formula VI in 30 ml of methanol. The reaction mixture is then poured into a 5% by weight aqueous solution of sodium in water. Extract with the aid of ethyl ether, dry the ethereal solution and leave^?add ether. An oily product is obtained which is distilled at 140 ° C under an absolute pressure of 0.04 ml of mercury and an amount of 4.7 g of oily product is obtained having the following formula:

OCH₃

<img file="RO91074A_D0004.tif" />

CH₂But

Heat for 3 hours at reflux temperature, a mixture of 0.1 ml acetyl chloride and a solution of 6 g (0.02 mol) of the product of formula VI in 30 ml of methanol. The reaction mixture is then poured into a 5% by weight aqueous solution of sodium carbonate in water. Extract with the aid of ethyl ether, dry the ethereal solution and evaporate the ether. This results in an oily product distilling at 140 ° C under an absolute pressure of 0.04 mm of mercury and thus obtaining an amount of 4.7 g of oily product of formula VII.

Heat for 3 hours at 170 ° C in an inert atmosphere, a mixture obtained by adding 4.2 g (0.01 moles) of the product of formula VII to 40 ml of dimethylsulfoxide containing sodium triazole salt. prepared starting from

1.6 g (0.024 mol) of triazole and 0.07 g (0.024 mol) of sodium hydride in 80% oily suspension.

The solution is then poured into 200 ml of water. Extract with the ethyl ether, dry the ethereal solution, evaporate. The residue is then purified by chromatography on a silica column. An amount of 3.1 g of oily product is thus obtained, consisting of a mixture in proportions similar and equal to the two diastereoisomers of the formula developed below:

OCHg

<img file="RO91074A_D0005.tif" />

B. Prepare the product of the following formula:

<td></td><td>Cl</td><td colspan="2">OH</td>

<td>z \₌</td><td>J &gt;</td><td>1 -C-CH₂-CH₂1</td><td>_ / · \a_</td>

<td></td><td></td><td>CH₂C1</td><td>IX</td>

by a process similar to that which allows the preparation of the product of formula VI, but the product chloromethyl- (orthoparadiclorphenyl)-ketone is used as a reagent instead of chlorophenyl- (parachlorophenyl) -ketone. Stir for 12 hours at ambient temperature, a mixture of 0.3 mol of product of formula IX, with 400 ml of aqueous sodium hydroxide solution with a weight concentration of 15%. The organic phase is diluted with ethyl ether, then separated by decanting, after which it is washed with water, dried and evaporated. A quantity of 64 g of a colorless, viscous, oily product is obtained by distillation, with the boiling point at a temperature between 147 and 150 ° C, under a reduced absolute pressure of 0.02 mm Hg column having the general formula:

Cl / / ° “ln ZX-C-CH₂CH₂-&lt;

^c O (X)

Heat for 110 hours at 110 ° C, a mixture of a solution of 5.8 g (0.02 mol) of product of formula X in 20 ml of normal butanol, in an amount of 1 , 4 g (0.02 mol) of triazole and 0.9 g (0.01 mol) of triazole sodium salt. Cool the reaction mixture to ambient temperature, dilute with water, extract with ether and then concentrate the ethereal solution. The residue is then purified by chromatography on a silica column, using a mixture of methanol, ethyl acetate and hexane in volumetric proportions of 5 and 47.5 and 47.5 respectively. Thus an amount of 5.1 g of product is melted at 131 ° C and which has the following formula:

<img file="RO91074A_D0006.tif" />

OH

-C-CH₂CH₂.

/

CIL-NN

O. /, \ OJ (XI)

A mixture of 0.10 ml of acetyl chloride with a solution of 3.1 g of product of formula XI in 30 ml of absolute ethanol is heated at reflux boiling temperature for 4 hours. Allow to cool. The crystals formed are filtered, washed with cold ethanol and thus obtain an amount of 1.2 g of white crystals that melt at 162 ° C and correspond to the most polar diastereoisomer (observed by thin layer chromatography) of the product with the following formula:

oc₂H₅

<img file="RO91074A_D0007.tif" />

(XII) = / CH₂-, - N

II

The mother waters obtained from this filtration are then concentrated and the residue is diluted with one ml of ethanol, followed by 2 ml of isopropyl oxide and then ⁴⁵ the crystals formed are separated. An amount of 0.2 g of the same diastereoisomer melting at a temperature of 164 ° C is thus obtained. By chromatography on a silica gel column of the oily residue obtained by⁵⁰ crystallization, a second amount of diastereoisomer, less polar, melting at 61 ° C is obtained.

If the radical Rj ^ is a hydrogen atom the compounds it contains ⁵⁵ 2 asymmetrical carbon atoms and the 2 diastereoisomers can be distinguished by chromatography on a thin layer of silica using a mixture of methanol, ethyl acetate and hexane in volumetric proportions. ⁸⁰ 5 and 20 and 75 respectively. The least polar compound migrates as high as in the case of chromatography and is noted with A. The highest polarity compound migrates the most _β5 down in the case of chromatography and is rated 13.

where the radical R₁ it is different from the hydrogen atom, the compounds have three asymmetric carbon atoms, thus there are four diastereomers. These diastereoisomers are sometimes difficult to separate by chromatography, but when they can be separated it is found that diastereoisomer A is less polar, diastereoisomer D is most polar, and diastereoisomers B and C have intermediate polarities.

The invention has advantages in that it makes a liquid composition for plant protection.