FR2560007A1 - FUNGICIDAL COMPOSITIONS COMPRISING PHENOXY BENZALDEHYDE DERIVATIVES - Google Patents

Abstract

THE INVENTION RELATES TO FUNGICIDAL COMPOSITIONS. ITS SUBJECT TO FUNGICIDAL COMPOSITIONS INCLUDING AS ACTIVE INGREDIENT AN EFFECTIVE QUANTITY OF AT LEAST ONE COMPOUND OF GENERAL FORMULA I: (CF DRAWING IN BOPI) OR X REPRESENTS HYDROGEN OR CHLORINE AND IN IT REPRESENTS HYDROGEN OR A NITRO GROUP. APPLICATION IN THE CONTROL OF FUNGAL DISEASES OF PLANTS.

Description

The present invention relates to fungicidal compositions and a

  method for fighting diseases

  fungal plants. More particularly, it is

  include fungicidal compositions comprising phenoxy benzaldehyde derivatives as an active ingredient and the use of these phenoxy benzaldehyde derivatives for controlling

  against fungal diseases of plants.

  According to the present invention, there is provided

  fungicidal compositions comprising as active ingredient in an effective amount at least one compound of the general formula I CF 3 o, x / 0 $ c (X) represents hydrogen or chlorine and

  Y represents hydrogen or a nitro group).

  General Formula I encompasses the following compounds: - (2-chloro-4-trifluoromethyl) phenoxy-2-nitrobenzaldehyde (Compound N 1); (2,6-dichloro-4-trifluoromethyl) -phenoxyl-2-nitro-benzaldehyde (compound N 2); 3 - / - (2-chloro-4-trifluoromethyl) -phenoxy-7-benzaldehyde (compound N 3) and

  3-E- (2,6-dichloro-4-trifluoromethyl) -phénoxy7-

benzaldehyde (compound N 4).

  These four compounds of the general formula I are known herbicides or - in the absence of results

  biological - their herbicidal effect is made probable.

  In the U.S. Patent No. 4,306,900 (priority date: March 5, 1979, application No. N 182,372), new nitro-diphenyl ether derivatives are protected as herbicides. Compounds N 1 and 2 are included in the

  field of protection of this U.S.

  In example 4 of this patent, the preparation of

  2-chloro-4-trifluoromethyl-3'-formyl-4'-nitro-diphenyl

  Ether is described (this compound is identical to the compound N 1, but another nomenclature is used), the yield, the melting point and the elemental analysis are indicated and in Table II the herbicidal effect of this compound is described. In this patent, the physical constants and the biological activity of the compound N 2 do not

are not indicated.

  In DOS No. 3,017,795, U.S.A .: 11 May 1979 (38,043) and 14 April 1980 (136,171); date of publication in the Federal Republic of Germany 13 November 1980-7, new phenoxy-phenyl-carboxyoxyimines are

  described. Intermediate products of the general formula

  Methods II used in the synthesis are mentioned as novel compounds having a herbicidal effect (page 18), methods for their preparation are also described, but physical constants and biological results are not indicated. The compounds N 1 and 2 are included in the context of the general formula II of this DOS. The intermediate products of the general formula II are prepared by first forming the intermediate products not comprising nitro group and then nitrating the products thus obtained. The physical constants of intermediate products that do not include a nitro group are not indicated and no biological effects are attributed to these compounds (page 34). Compounds N 3 and 4 -3 - belong to the group of these intermediate products

not including a nitro group.

  In European Patent Publication No. 0 053 321 L priority: November 28, 1980 (DE 3 044 810), date of publication in the Federal Republic of Germany: June 9, 1982 (Patentblatt 82/23) 7, new herbicidal derivatives

  of phenoxy cinnamic acid are described. Derivatives of -

  phenoxy-2-nitro-benzaldehyde N 1 and 2 and also the substituted phenoxy-benzaldehyde derivatives N '3 and 4 are mentioned as intermediate products of the synthesis,

  but they are not attributed a herbicidal effect.

  In European Patent Publication No. 0 064 658

  / priority: 9 May 1981 (DE 31 18 371); date of publication

  in the Federal Republic of Germany: November 17, 1982, Patentblatt 82/46 /, are described new phenoxy

  benzaldehyde acetals having a herbicidal and

  plant growth. In their synthesis, we

  lists as an example 5- / F (2-chloro-4-trifluoro-

  methyl) -phenoxy-2-nitro-benzaldehyde and 5 - / - (2,6-

  dichloro-4-trifluoromethyl) -phenox-2-nitro-benzaldehyde, but no herbicidal effect is attributed to these compounds (see U.S. Patent No. 4,306,900). These two products

  intermediates are identical to the compounds N 1 and 2.

  It appears from the above patents that among

  the four compounds corresponding to the general formula I, -

  the compounds N 1 and 2 (substituted phenoxy-4-nitro-benzaldehydes) have a herbicidal activity, but biological results have been described only for the

compound No. 1.

  By conducting tests with phenoxy benzaldehyde

  substituted hydros, it has been found that, surprisingly,

  N 1-4 compounds exhibit activity

  fungicide. This finding is all the more surprising

  According to the most recent prior art and on the page (particularly in view of US Pat. No. 4,306,900 and DOS No. 3,017,795), those skilled in the art could have only drawn the conclusion substituted phenoxy benzaldehydes and their nitro derivatives

  had herbicidal properties.

  In the book by R. Wegler: "Chemie der Pflanzen-schutz- und Schddlingingsfmpfungsmittel", Vol. 5, Seringer-Verlag Berlin, Heidelberg New York 1977 (pages 73-82 and 401-407), it is taught that "diphenyl ethers" (substituted phenoxy benzene derivatives) are herbicides useful in

soy, maize and rice.

  The fungicidal compositions of the present invention comprise as active ingredient an effective amount - usually 0.00001-99% by weight - of at least one compound of the general formula I in admixture with suitable inert solid or liquid carriers,

  diluents and / or other auxiliary agents.

  The known compounds of the general formula I can

  be prepared by methods known per se.

  The preparation of these active ingredients is shown in

the following examples.

  3- (2,6-dichloro-4-trifluoromethyl) phenoxy-7-benzaldehyde (compound N 4)

  From 6.1 g (0.05 mole) of 3-hydroxy-

  benzaldehyde and 2.8 g (0.06 mol) of potassium hydroxide in 150 ml of anhydrous methanol under

  inert, the potassium salt of 3-hydroxy-

  benzaldehyde. The methanol is removed from the homogeneous solution

  by distillation under vacuum of the water pump and 2.5 g of potassium carbonate, 50 ml of dimethylsulfoxide and 13.75 g (0.055 mol, 10% molar excess) of 3.4 are added to the residue, 5-trichlorobenzotrifluorure. The reaction mixture is heated at 140 ° -144 ° C. for 8 hours.

  by stirring, the dimethyl is distilled off

  sulfoxide, 150 ml of benzene are added to the residue and the suspension is stirred for one hour. The solid material insoluble in benzene is filtered off and the filtrate is evaporated under the vacuum of the water pump. The residue is crystallized from a 1: 1 mixture of methanol and isopropanol. This gives 9 g of

  desired compound, 60% yield. Melting point: 49-50C.

White crystals.

Gross formula: C14H7C12F302

Molecular weight: 335 (calculated).

  The mass spectrum contains the characteristic fragments

  compounds comprising two chlorine atoms.

  m / e (r.i,) = 336/580 / = F3C / C1 / 2C6H20C6H4CH0

335/37, / - 3C- / C! -6H2 5 H & O

334/1000 / F 3 / / 2C6H2Cr6H4CO

333/370 / = F3C / C1 / 2C6H20C6H4CHO

271/520 / = F C / Cl / C6H20C6H5

3 6 2 6 5

236/560 / = F3CC6H2OC6H5

  -1 In the IR spectrum, the band appearing at 1690 cml is characteristic of the vCO vibration of the group

formyl.

  3 - / - (2-chloro-4-trifluoromethyl) -phenoxy7-

  Benzaldehyde (compound N 3) is prepared in an analogous manner. (2,6-Dichloro-4-trifluoromethyl) -phenoxy-2-nitro-benzaldehyde (Compound N 2)

  3.75 g (0.011 mol) of 3 - / - (2,6-dichlorobenzene) are dissolved in

  4-trifluoromethyl) -phenoxy-7-benzaldehyde in a mixture of 8.6 ml of dichloromethane and 5.3 ml of acetic anhydride, after which nitrating acid prepared from 2.4 ml (0.034 mol) of 65% nitric acid and 2.4 ml of 98% sulfuric acid is added dropwise while stirring at a rate such that the

  system does not exceed 10 C. After the completion of the

  After stirring, the stirring is continued at room temperature for 3 hours, after which the dichloromethane is removed under water-jet vacuum and the residue is poured into ice water. The powdery substance

  precipitated white is separated by filtration and dried.

  2.7 g of the desired compound are thus obtained in the form of white crystals, yield 64%. Fusion point:

117-119 C.

Gross formula: C14H604C12F3

Molecular weight: 379 (calculated).

  The mass spectrum of the product indicates to each fragment the ratio of isotopes characteristic of compounds

comprising two chlorine atoms.

  m / e (r.i.) = 381/720 / = F3C / Ci / 2C6H2oC6H3 / NO / CHO

9 3C 2 6H20C6H3 / N / CHO

  379/1000 / = F 3C / C1 / 2C5H20C6H3 / NO / CHO

349/650 / = F3C / C / 2C6H20C6H3 / O / CHO

285/320 / = F2C / Cl / 2C6H20C6H4

230/220 / = F3C / C1 / 2C6H20H

  Under the effect of internal circular currents, the

  Aromatic aldehyde species appear at high delta values, between 9.6 and 10.5 ppm. The aldehyde proton of the starting material is found at 9.85 ppm while the nitro derivative gives a signal under the action

the inducing effect at 10.35 ppm.

  The band appearing at 1690 cm in the spectrum is

  characteristic of the VCO vibration of the formyl group.

  The spectroscopic results prove without ambiguity that in the nitration conditions, the oxidation of the group

  Formyl to a carboxy group does not occur.

  5- (2-Chloro-4-trifluoromethyl) is prepared

  phenoxy-2-nitro-benzaldehyde in a similar manner.

  The fungicidal compositions of the present invention

  can be prepared in a manner known per se.

  Thus, the compositions of the present invention can

  for example wettable powders (PM),

  suspended suspension concentrates (CS), water-miscible solution concentrates (CM), emulsifiable concentrates (EC), very small volume compositions (TPV) or sheets, preferably seedlings. These compositions can be prepared by mixing the active ingredient (s) with solid or liquid inert carriers, solvents and possibly other auxiliary agents. These auxiliary agents may be, for example, surface-active agents, for example wetting agents, suspending agents, dispersants, emulsifiers, or agents which prevent coagulation, anti-agglutination agents,

  agents that promote membership, agents of

  penetration agents and

  which maintain or enhance the biological effect, antifoaming agents, etc. Useful solid and diluent vehicles are

  inactive mineral substances (eg china

  clay, kaolin, porcelain earth, attapulgite, montmorillonite, mica flakes, pyrophilite, bentonite, infusorial earth, highly dispersed synthetic silicic acids, calcium carbonate, magnesium calcine, dolomite, gypsum, tricalcium phosphate, fulling earth, etc.). Other solid and diluent vehicles that can be used are crushed tobacco stalks, wood flour, etc.

  Liquid vehicles, thinners and solvents used

  sands are: water, organic solvents, mixtures of water and organic solvents, for example methanol, ethanol, new isopropanol, diacetone alcohol, benzyl alcohol, glycols as

  ethylene glycol, triethylene glycol and propylene

  glycol; esters of the above compounds, for example methyl cellosolve, butyl diglycol; ketones, for example dimethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .; esters, by

  for example, ethyl acetate, acetates of n- and iso-

  butyl, amyl acetate, isopropyl myristate, dioctyl phthalate, dihexyl phthalate, etc .; aromatic, aliphatic, alicyclic hydrocarbons, such as paraffinic hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetralin, decalin, alkyl mixtures

  benzenes; chlorinated hydrocarbons, for example tris

  chloroethane, dichloromethane, perchlorethylene, dichloropropane, chlorobenzene, etc .; lactones, for example gammabutyrolactone, etc .; of the

  lactams, for example N-methyl-pyrrolidone, N-

  cyclohexyl-pyrrolidone; acid amides, for example

  dimethylformamide, etc .; oils of vegetable origin

  animal or animal, for example,

  nesol, flax seed oil, rapeseed oil, olive oil, soybean oil, castor oil and spermaceti oil, etc. Suitable wetting, dispersing and emulsifying agents and also adhesion increasing and aggregation preventing agents and spreading agents can be used.

  be of an ionic or non-ionic character.

  The ionic agents may be, for example, salts of various saturated or unsaturated carboxylic acids; aliphatic, aromatic hydrocarbon sulphonates or

  aliphatic-aromatic; sulphates of alcohols

  lactic, aryl or aralkyl; alkyl, aryl and aralkyl sulfonates, esters and ethers; sulphonates of condensation products

  phenol, cresol and naphthalene; sulphate oils

  muck of vegetable or animal origin; alkyl esters

  lactic, aryl and aralkyl phosphoric acid; and salts of the above compounds formed with alkali or alkaline earth metals or organic bases (by -9-

  salts with amines or alkanol-

  amines). Preferable examples of these surfactants

  Ionic actives are the following compounds: sodium lauryl sulphate, 2-ethyl hexyl sulphate; sodium salts, ethanolamine, diethanolamine, triethanolamine

  amine and isopropylamine of dodecylbenzene

  sulfonic; mono- and diisopropylnaphthalenesulphonate

  sodium; the sodium salt of the naphthalene acid

  sulfonic acid and sodium diisooctyl sulfosuccinate; sodium xylenesulphonate; sodium and calcium salts of petroleum sulfonic acids, potassium soaps, potassium, sodium, calcium, aluminum and magnesium stearates, etc. The phosphoric esters may be ethers of alkyl phenols or fatty alcohols phosphates formed with a polyglycol and

  forms of the above compounds partially or completely

  neutralized by the organic cations or bases

  above. Other anionic surfactants that may be used are disodium N-octadecyl sulphosuccinate,

  sodium-N-oleyl-N-methyl-tauride and various

  sulfonates. Suitable nonionic wetting, dispersing and emulsifying agents are ethylene oxide ethers

  formed with C10-20 alcohols, such as stearyl

  polyoxyethylene, oleyl-polyoxyethylene; ethers formed with alkyl phenols, for example ethers

  of polyglycol formed with tert-butylphenol, octyl-

  phenol or nonylphenol; esters formed with organic acids, for example stearic acid or myristic acid esters formed with polyethylene glycol or polyethylene glycol oleate, etc .; block polymers of ethylene oxide and propylene oxide; partial esters of fatty acids and oleic acid formed with hexitol anhydrides, for example sorbitol esters formed with oleic acid or stearic acid; Condensation products of these compounds formed with ethylene oxide; tertiary glycols, for example

  3,6-dimethyl-4-octyl-3,6-diol or 4,7-dimethyl-

  -décyne-4,7-diol; polyethylene glycol thioethers, for example dodecyl mercaptan ethers formed with polyethylene glycol, etc. Suitable adhesion improving agents are alkaline earth metal soaps; salts of sulfosuccinic acid esters; natural and artificial macromolecules soluble in water, for example casein, starch, vegetable gums, gum arabic,

  cellulose ethers, methylcellulose, hydroxyl

  ethylcellulose, polyvinylpyrrolidone, polyalcohol

  vinylic, etc. Suitable antifoam agents are

  block polymers of polyoxyethylene or polyoxypropyl

  low molecular weight lene (in which the number of octyl, nonyl and phenylpolyoxyethylene / ethylene oxide meshes is greater than 5); long chain alcohols, for example octyl alcohol, etc .; oils

special silicone, etc. -

  Suitable additives may also be added to render the prepared compositions chemically-colloidally compatible with various fertilizer systems. The fungicidal compositions of the present invention may also include known pesticides and / or

nutrient constituents.

  The wettable powders (MW) can be prepared by mixing the active ingredient (s), the auxiliary agent (s) and the surfactant (s) with the vehicles and finally grinding and homogenizing the mixture. If liquid surfactants are used, it is also possible to proceed by applying the liquid surfactant to the solid organic or inorganic carrier (s) or to the powder mixture comprising:

  the solid active ingredient (s) by spraying.

  This method is also applicable for ingredients

liquid assets.

  If liquid surfactants are used, it is also possible to suspend the solid components which have been premilled in an organic solvent which contains the liquid surfactant (s). The suspension thus obtained can be dried, for example by spraying. Thus, the surfactant is applied to the surface of the solid active ingredient

or solid vehicle.

  An emulsifiable concentrate (EC) can be prepared by dissolving the active ingredient or a mixture of these ingredients in the presence of a surfactant above in a solvent immiscible with water. The emulsifiable concentrate thus obtained forms with water spontaneously or with the use of a weak mechanical action a ready-to-use spraying material which remains unchanged even after a long period of storage. We can prepare

  a solution in solution miscible with water (CM) in

  solvent the active ingredient in water and / or in a

  solvent miscible with water in the presence of an auxiliary agent

  soluble water soluble agent. By dilution with water, a sprayable material having the

desired concentration.

  Concentrates of the active ingredient in aqueous solution may also be dispersed in water immiscible solvents by appropriate choice of the emulsifier; so-called inverse emulsions are obtained. Thus, by appropriate choice of the solvent and surfactants, compositions can be prepared.

  which by mixing with water or with non-liquid

  miscible with water form dispersed systems -

  sometimes molecularly dispersed - which remain

  unchanged for a longer period.

-12-

  Suspended Concentrations (CS) are prepared in

  solvent wetting and dispersing agents in a mixture of water (preferably treated by ion exchange)

  and an antifreeze component (preferably ethylene

  glycol or glycerol) if necessary by heating. To the solution thus obtained, one adds, while agitating constantly,

  the solid active ingredient (s) (powder or cris-

  tallins) and, if necessary, the anti-

  agglutination (eg Aerosil 200). The particle-liquid phase system thus obtained (slurry) is milled in a wet grinding apparatus (for example a closed Dyno mill) to the desired particle size, preferably not more than 5 microns,

  in order to achieve proper storage stability.

  After grinding, an antifoaming agent or a thickening agent (eg Kelzan S) is added by homogenizing, if desired. It is also possible to proceed by changing or modifying the order of addition of the constituents or by adding other constituents (for example dyes) if necessary. In addition to the solid active ingredient, it is also possible to use as associates in combination active ingredients immiscible with water or miscible with water. Active ingredients having a low melting point may be added in the molten state in the presence or

in the absence of an emulsifier.

  Very small volume compositions can be prepared in a manner similar to CE compositions

and in some cases CS forms.

  Granules suitable for direct use (G) may be prepared by extrusion, or by lamination

  using a granular vehicle (eg

  crushed brine), absorbing the liquid component

  a vehicle having an absorption capacity.

  Usable granules for atomization (GA) can be prepared from a wettable powder form and / or suspended concentrate by an agglomeration technique (for example in a dragee tank using a binder)

  The active ingredient content of the fungal compositions

  of the present invention is generally 0.0001-

  99% by weight, preferably 0.01-95% by weight. Sprayable materials and dusting powders

  ready to use can be prepared from

  above positions by dilution with water or an inert solid diluent in a known manner. The active ingredient content of the ready-to-use compositions is generally 0.0001-10% by weight, preferably 0.01-5% by weight. It is also possible to mix before use the sprays prepared from several compositions each containing a single

active ingredient.

  Seed leaves are a preferred embodiment of the compositions of the present invention. Seed leaves are prepared by incorporating the ingredient

  active in the leaf or in the seeds.

  According to another feature of the present inventicm

  a method of combating fatal diseases is provided for

  plants which includes the application of a quantity

  effective use of at least one compound of the general formula I on plants, or harmful fungi or

their environment.

  The composition of the main types of fungal agents

  The present invention is described below. The

  quantities should be understood as being in% by weight.

  Suspended Concentrate (CS) Compound N 4 40.0% Ethylene Glycol 10.0% Nonylphenyl Polyglycol Ether (10 EO) 5.0% Polysaccharide (Xanthan Gum) 0.1% Silicone Oil 1.0% Water 43.9% -14- Wettable Powder (PM) Compound N 1 30.0% Silicic acid highly dispersed 15.0% Chinaclay 20.0% Sodium lignosulfonate 5.0% Diatomaceous earth 25.0% Dispersing agent 5.0% Granules (G) Compound N 3 5.0% Crushed limestone 69.0% Ethylene glycol 3.0% Calcium lignosulfonate 3.0% Highly disperse silicic acid 5.0% Water 15.0% Granules s dry runners usable for spraying (GA) Compound N 4 80.0% Mixtures of anionic and nonionic emulsifiers 2.0% Dispersing agent 7.0% Water 3.0% Amulsifiable concentrate (EC) Compound N 2 20 0% Xylene 50.0% Cyclohexanone 12.0% Isophorone 10.0% Polyoxyethylene sorbitol monooleate 5.0% Sodium lignosulfonate 3.0% Seed film a) Preparation of the sheet 80 g of polyvinyl alcohol are added only the type RHODOVIOL 4/125 P (the viscosity of a 4% aqueous solution is 4 cPo at 20 C; hydrolysed at 89 mol%) to 615 g of water (60 ° C.) with stirring. After dissolution, 20 g of polyvinyl alcohol of the type RHODOVIOL / 20 m (the viscosity of a 4% aqueous solution is 30 cP at 20 ° C., hydrolyzed at 98 mol%) and 20 g of glycerol are added to the solution. The mixture is stirred vigorously until a homogeneous solution is obtained. The solution is allowed to stand for 24 hours so that the bubbles leave the solution. The solution is extended on a one-layer glass plate having a thickness of 0.50 mm by the stripping blade method and dried at room temperature. The sheet thus obtained peels off the glass plate; thickness 0.05-0.06 mm (control sheet). b) Preparation of a sheet comprising the active ingredient The procedure is as in paragraph a), except that the solution used for pouring the sheet is added

  0.120 g of compound N 2 suspended in 5 ml of water.

  After removal of the bubbles, a sheet is dried which is dried. The sheet thus obtained is similar to that according to paragraph a), but comprises 1000 ppm of compound

N 2 as active ingredient.

  As an active ingredient instead of the compound N 2,

  it is also possible to use a suspension of 0.0120 g of

laid N 4 and 5 ml of water.

  The active ingredient content of the sheet is ppm. Seed treatment, spraying and dusting are the most common methods of fighting and controlling fungal diseases by protecting

  chemical plant. The composition comprising the

  fungicidal active ingredient is preferably applied to part or the environment of the host plant subject to

  to infection or threatened by it.

  Seed treatment can be used for the preparation of infection-free seeds and to fight

  against soil fungi that infect the seeds.

  Seeds and seedlings are first of all threatened by conidial fungi -16- (eg Fusarium graminearum and Fusarium monoliforme and Nigrospora oryzae in maize cultivation and strains belonging to the genera Rhizoctonia, Penicillium

and Helminthiosporum).

  Standing crops can be protected against fungal infections that threaten leaves and

  plant fruits for example by spraying or sau-

  powdering. As fungal diseases, for example, Monilia fructigena and Spilocea pomi (Fusicladium dendriticum) can be mentioned on apples or Botrytis cinerea on grapes. The fungicidal compositions of the present invention can be used for example against fungi

following: - a) Family Moniliaceae: Genus Species Monilia (eg M.

  fructigena) Aspergillus (eg A. niger) Penicillium (eg P. crustaceum) Botrytis (eg B. cinerea) Verticillium (eg V. albo-atrum) Trichothecium (eg T. roseum) Cercosporella (eg C. herpotrichoides) b) Family Dematiaceae: Genus Strain Thielaviopsis (eg T. basicola) Nigrospora (eg N. oryzae) Spilocea (eg S. pomi, szinonim Fusicladium dendriticum) Cladosporium (eg C. fulvum) Helminthosporium (eg H. turcicum) Cercospora (e.g. C. beticola) Alternaria (e.g. A. solani) Stemphylium (e.g. S. radicinum) -17- c) Tuberculariaceae family: Genus Fusarium strain (e.g. F, graminearum and F. oxysporum) In the following examples of activity, the effect of the compositions of the present invention is compared to that of 1,2,5,6-tetrahydro-N- (trichloromethylthio) phthalimide.

(Captan), a known fungicide.

Example 1

  Fungicidal Activity Assays An agar plate is prepared by casting a potato agar nutrient medium containing 2% dextrose into a petri dish (100 mm diameter) and

  leaving the nutrient medium to solidify.

  An emulsifiable concentrate having an active ingredient content of 20% is diluted to the desired concentrations. A suspension comprising a number of spores which corresponds to the isolated experimental fungi is prepared at a dilution such that when 1 drop of the spore suspension is placed on the glass slide of the microscope at a magnification of 100-160, 25-30 spores appear in the visual field, taking the average

from 5-50 visual fields.

  A quantity of 1 ml of the spore suspensions thus obtained is added to the pipette to 1 ml of the active ingredient solution, the mixture is left for 30 minutes and applied to the agar plate. The fungi are inoculated until vigorous development begins, after which the results are evaluated by comparing the development of the treated samples to that of the control according to the following scale: 1 = no colony development (0% relative to control) 2 = poor colony development (10% compared to control)

25600O?

  3 = average development of the colonies (50% relative to the control) 4 = significant development of the colonies (100% compared to the control)

  The results are summarized in Table 1.

Table 1

* Fungicidal activity against Aspergillus niger (A) and Botrytis cinerea (B) Cam- Concentration Colon development Development Fungicidal activity, planted in colony-scale ingredients,% N active, Repeated tests% mean ppm (A) (B) 1 2 3 4 mean 1 2 3 4 mncyenne (A) (B) (A) (B)

  10000 1 1 1 1 1 1 1 1 1 1 0 0 100 100

  2000 1 1 1 1 1 '1 1 1 1 1 0 0 100 100

  1,400 2 2 2 2 2 2 2 2 2 2 2 10 10 90 90

2 3 2 3 2,5 3 3 2 2 2,5 30 30 70 70

  16 4 3 4 4 3.75 4 3 4 3 3.5 82-83 75 17-18 25

10000 1 1 1 1 1 1 1 1 0 0 100 100

2000 1 1 1 1 11 1 i 1 0 0 100 100

  2,400 2 3 2 3 2,5 2 2 2 2 2 30 10 70 90

  3 3 3 2 2,75 2 3 3 2 2,5 40 30 60 70

  16 3 4 4 4 3,75 3 3 4 "4 3,5 82-83 75 17-18 25

  10000 2 2 2 2 2 22 2 3 2 3 2.5 10 30 90 70

  2000 3 3 3 3 3 3 3 3 3 3 3 50 50 50 50

  3 400 4 4 4 4 4 4 4 4 44 4 4 100 100 0 0

3 2 2 3 2,5 2 2 2 2 2 30 10 0 0

  16 3 3 4 4 3.5 3 3 3 4 3.25 75 62-63 0 0

  10000 2 2 3 3 2.5 3 3 3 3 3 30 30 70 70

  2000 3 4 3 4 3.5 4 3 3 4 3.5 75 75 25 25

  4 400 4 4 4 4 4 4 4 4 4 4 4 100 100 0 0

4 4 4 4 4 4 4 44 4 4 100 100 0 0 ru

16 4 4 4 4 4 4 4 4 4 4 100 100 0 0

  ... o Gold Table 1 (continued) Com- Concentration Colony development Development Fungicide activity, ingredient-wise in colony-scale numbers% N active, Repeated tests% mean ppm (A) (B) 1 2 3 4 average 1 2 3 4 monyenne (A) (B) (A) (B) Standard 10000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 Captan 2000 1 11 1 1 1 1 1 1 0 0 100 100 ..DTD: 400 2 2 2 2 2 2 2 2 2 2 10 10 90 90

2 3 2 3 2,5 3 2 3 2 2,5 30 30 70 70

  16 3 3 4 4 3.5 4 3 4 3 3.5 75 75 25 25

  0 Blank test - 4 4 4 4 4 4 4 4 4 100 100 0 0 0% CJ o O O O

-21-. 2560007

Example 2

  Fungicidal test in liquid culture The active ingredient is emulsified in 20 ml of a nutrient medium containing 2% malt in the desired concentration, after which the nutrient medium is inoculated into the nutrient medium.

  experiment pinion. The rate of inhibition of the development

  colony development is determined after an incubation period of 7 days. The concentrations necessary for complete inhibition of development are

shown in Table 2.

Table 2

  Concentrations for fungicidal effect in ppm Genus Standard N of the active ingredient Captan 1 2 3 4 Fusarium oxyspcrum 300 300 300 1000 1000 Fusarium nivale 300 300 300 1000 1000 Fusarium solani 300 300 300 1000 1000 Alternaria solani 100-300 300 300 1000 1000 Aspergillus niger 100-300 100-300 300 1000 1000 Botrytis cinerea 100-300 100-300 100-300 1000 300 Botrytis fabae 100-300 100-300 10C-300 1000 300 Cercospora beticola 100-300 100-300 100-300 1000 300 Stemphylium radicinum 100-300 100-300 100-300 1000 300 Trithothecium roseun 100-300 100-300 3C-100 300 300 Thielaviopsis basicla 100-300 30-100 30-100 100-300 100-300 -22- Table 2 continued Genus Standard N of the active ingredient Captan 1 2 3 4 Nigrospora oryzae 30-100 30-100 30-100 100-300 100-300 Cladosporium cucumerinum30-100 30-100 30-100 100-300 100-300 Penicillium crustaceum 30- 100 30-100 30-100 100-300 100-300 Verticillium alboatrum 30-100 30-100 30- 100 100-300 100-300 Fusicladium dendriticum 30 30 30-100 100-300 100-300 Monilia fructigena 30 30 30 100-300 100-300

Example 3

  Phytotoxicity tests in the greenhouse Cultivation trays with a surface of 1.64 dm are filled with sandy soil and 20 to 30 seeds (depending on the experimental plant) are sown in two

  identical tests in furrows 0.5-1.0 cm wide

  founder. Ten days after plant growth, ready-to-use sprays prepared from an emulsifiable concentrate containing 20% of the ingredient

  are applied to young plants at a concentration

  corresponding to doses of 1, 3 and 9 kg of

  active ingredient per hectare, respectively, using a laboratory sprayer. Percentages of damage

  plants are determined 10 days after the spraying.

  tion. The results are summarized in Table 3.

  The following experimental plants are used: A = soy (Glycine soya) B = autumn wheat (Triticum aestivum) C = autumn barley (Hordeum vulgare) D = males (Zea mays) E = millet d Italy (Setaria italica) F = cotton (Gossypum hirsutum) G = white mustard (Sinapis alba) H = bean (Phaseolus vulgaris) I = pea (Pisum sativum) K = lupine (Lupinus albus) L = large bean (Vicia faba) M = alfalfa (Medicago sativa) N = carrot (Daucus carota) O = beet-sugar (Beta vulgaris) P = sunflower (Helianthus annuus) 0 L OS 0C 8 O9 O07o9 S0 01 L OS 0O d 0 SL OS Z 09 OiZ Where Z Sl OO 0T0T o 0 s9 OOz 09OE 06OL0u OLO? OT N

  0 56 09 0d 06 OS 0 6 08 OL 001 0609 W OZ

0 S G OZ SL OSZ 001 0609 0608 OL 1

0 SZ OZ OOTOZ O10L 09 OS 0L007 X

  0 0O 0 0 07 O0OT09 0t 0T O 0ú If I

0 O SI OS 01 0 8 S9 08 08 OS H

  0 56 09 Sú 0 ú 0OC5608 0506 09 o7 0 0 OO O o O O O O 06S9 0ú86 6 08

  0 OO OLOC 001 09 O001 SL0O OO 08 09 3

  0 OS 0úO? S OZ SI OLO úO 09 0 oT a 0 0 Oeo 010 OZ 010 I OSOS 01 D

0 SZ 5 0 OZ 0 0 0 0O 1 S E O

O S 0 O 0 0 T 5 0 01 S O V

6 C 1 6u 1 6 ú1 6 ú T

  ## EQU1 ## soNnnoi; T4D; ueTP9.zb eiDd 9PTOTXOIOAzld ap STeSSa ú neIlq0e

ZOOO9SZ

-25-

Example 4

  Soybean fungal disease protection by seed treatment Seed treatment is carried out using a suspension concentrate of 400 grams per liter of the active ingredient and a 50% wettable powder form of Captan as a control, respectively; 0.1, 0.25, 0.5, 1.0 and 2.0 g / kg of active ingredient are applied to the seed surface of the Merit soybean type. The percentages of germination and fungal infection are determined in

  a laboratory 10 days after seed treatment.

  In field experiments, plots are sown on April 20 (depth: 4-5 cm); distance between stems: 5 cm; distance between lines: 50 cm. When the height of the soybean plants is 10-12 cm, the plants grown are counted and the result is expressed as a percentage of the untreated control. The results

are summarized in Table 4.

Table 4

  Soy Seed Treatment Test N Dose of% Infection of Seeds% of Germi- Number of Plants in the Ingredient Ingredient of Alternaria Penicillium Fusarium Nation in Field, in% Relative Active Active, g / kg sp . sp. sp. witness laboratory

0.1 28.1 5.0 2.2 85 105

0.25 14.2 3.2 1.3 90 118

1 0.5 7.0 - 0.5 80 120

1 4.3 - - 70 94

2 1.5 - - 64 92

0.1 22.3 5.8 3.1 80 102

0.25 14.1 4.4 1.2 85 104

2 0.5 6.6 0.2 - 92.122

1, 4.2 - - 78%

2 0.5 - - 66 90

0.1 58.2 8.9 6.2 82 100

0.25 49.5 7.6 5.0 82 105

3 0.5 13.4 3.8 1.8 86 107

1 6.6 2.0 0.2 90 105

2 4.3 0.5 - 82 98

0.1 54.2 9.1 5.0 80 101

0.25 39.8 6.8 4.4 82 102

4 0.5 16.3 2.2 2.3 86 109

1 9.8 1.5 - 91 102

2 6.7 - - 84 102

  LM o, O, O, Table 4 (cont'd) Seed% of seed infection% of germnni- Number of plants in the ingredient the ingredient Alternaria Penicillium Fusarium nation in field, in% relative active active , g / kg sp. sp. sp. witness laboratory

0.1 26.4 3.2 3.0 82 102

0.25 13.6 2.2 1.5 90 116

  Standard 0.5 7.5 0.2 0.5 94 121 Captan 1 2.6 - - 90 114

2 0.8 - - 90 105

  0 Blank test - 75.0 12.0 6.0 78 100 I -4 LI o l to t; -28-

Example 5

  Protection against Fusarium head blight in winter wheat The trials were carried out on plots (10 m) on quadruple autumn wheat (Jubilejnaja). From N-1-4 compounds emulsion concentrates, ready-to-use spraying materials are prepared and sprayed at the end of the spike at doses of 1, 2 and 3 kg of active ingredient per hectare. , respectively,

  with watering at a rate of 500 liters of water per hectare.

  Fusarium infection of ears is determined 12 days

  after spraying, evaluate 200 ears per plot.

  The product of each plot is weighed after harvest and the total and internal Fusarium seed infection is determined based on an average sample of

200 seeds per plot.

  The results are summarized in Table 5 and expressed as the average of four identical assays. C> o rcre C4 e m0c r- p u) CbDcOD CD00 0e.D'or-oc C c

tOr s * b..b.N.b. = O.b.b.

  taZ- UILfll.O% 04UL- A LO LO (U) Lfl Ln., '4Lq'; CoCn ul ao Wr. ## EQU1 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## uo (y 0 C w - Co a ZH (COLC 0n aC YDL) C -30-

Claims (7)

  1. A fungicidal composition comprising as active ingredient in an effective amount at least one phenoxy benzaldehyde derivative of the general formula I CF 3 Cl 0 / I /   Wherein Y represents hydrogen or chlorine and Y represents hydrogen or a nitro group   in admixture with at least one auxiliary agent or diluent.   2. A fungicidal composition according to claim 1, characterized in that it comprises as active ingredient   3- [(2-chloro-4-trifluoromethyl) phenoxy] benzaldehyde.   3. A fungicidal composition according to claim 1, characterized in that it comprises as active ingredient   3- [2,6-dichloro-4-trifluoromethyl] phenox] -7- benzaldehyde.   4. A fungicidal composition according to claim 1, characterized in that it comprises as active ingredient   5-f (2-chloro-4-trifluoromethyl) phenoxy-2-nitro-   benzaldehyde. 5. A fungicidal composition according to claim 1, characterized in that it comprises as active ingredient -31-   5-L- (2,6-dichloro-4-trifluoromethyl) -phenoxyl-2-nitro-   benzaldehyde. 6. A method of controlling fungal diseases of plants, characterized in that at least one compound of the general formula I (where X is hydrogen or chlorine and Y is hydrogen or a group) nitro) in an effective amount on the plants or on the place o   they grow or their environment.   7. The use of phenoxy benzaldehyde derivatives of the general formula I (where X represents hydrogen or chlorine and Y represents hydrogen or a nitro group) for the protection of plants against fungal diseases.