GB2152817A

GB2152817A - Fungicidal compositions comprising phenoxybenzaldehydes

Info

Publication number: GB2152817A
Application number: GB08501041A
Authority: GB
Inventors: Jozsef Bakos; Balint Heil; Laszlo Kollar; Szilard Toros; Gyula Eifert; Ferenc Bihara; Mihlay Pletyak; Anna Durko; Istvan Kuronya; Istvan Magyari; Judit Timar; Peter Bohus; Laszlo Wohl
Original assignee: Budapesti Vegyimuevek Rt
Current assignee: Budapesti Vegyimuevek Rt
Priority date: 1984-01-17
Filing date: 1985-01-16
Publication date: 1985-08-14
Also published as: GB2152817B; GB8501041D0; HU190222B; CS248732B2; DD229013A5; HUT36332A; JPS60231602A; DE3501426A1; FR2560007A1; CH663321A5

Abstract

According to the present invention there are provided fungicidal compositions comprising as active ingredient an effective amount of at least one compound of the general Formula I <IMAGE> wherein X stands for hydrogen or chlorine and Y represents hydrogen or nitro.

Description

SPECIFICATION Fungicidal Compositions This invention relates to fungicidal compositions and a method for combating fungal diseases of plants. More particularly it is concerned with fungicidal compositions comprising phenoxy benzaldehyde derivatives as active ingredient and the use of the said phenoxy benzaldehyde derivatives to combat fungal diseases of plants.

According to the present invention there are provided fungicidal compositions comprising as active ingredient in an effective amount at least one compound of the general formula I

(wherein X stands for hydrogen or chlorine and Y represents hydrogen or nitro).

The general Formula I encompasses the following four compounds: 5-[(2-chloro-4-trifluoromethyl)-phenoxy]-2-nitro-benzaldehyde (Compound No. 1); 5-[(2,6-dichloro-4-trifluoromethyl)-phenoxy]-2-nitrobenzaldehyde (Compound No. 2); 3-[(2-chloro-4-trifluoromethyl)-phenoxy]-benzaldehyde (Compound No. 3) and 3-[(2,6-dichloro-4-trifl uoromethyl)-phenoxy]-benzaidehyde (Compound No. 4).

The said four compounds of the general Formula I are either known herbicides or-in the absence of biological data-the herbicidal effect thereof is rendered probable.

In US Patent specification No.4,306,900 (priority date: 5th March 1979, USA, No. 182,372) new nitro-diphenyl ether derivatives are protected as herbicides. Compounds Nos. 1 and 2 fall under the scope of protection of the said US patent.

In Example 4 of the US patent specification referred to the-preparation of 2-chloro-4-trifluoromethyl-3' formyl-4'-nitro-diphenyl-ether is disclosed (this compound is identical with compound No. 1 but another nomenclature is used), the yield, melting point and elementary analysis are disclosed and in Table II the herbicidal effect of the said compound is described. In the said patent specification the physical constants and biological activity of Compound No. 2 are not disclosed.

In DOS No. 3,017,795JUS priorities: 11th May 1979 (38,043) and 14th April 1980(136,171); publication date in the German Federal Republic 13th November 1980], new herbicidal phenoxy-phenyl-carboxyoxyimines are described. The-intermediates of the general formula Il used in the synthesis are mentioned as new compounds having herbicidal effect (page 18), the methods for their preparation are set forth too, but the physical constants and bidlogical data are not disclosed. Compounds Nos. 1 and 2 fall under the scope of the general Formula ll of the said DOS.The intermediates of the general Formula II are prepared by first forming the intermediates comprising no nitro group and subsequently nitrating the products thus obtained. The physical constants of the intermediates comprising no nitro group are not disclosed and no biological effect is attributed to these compounds (page 34). Compounds Nos. 3 and 4 belong to the said intermediate group comprising no nitro group.

In European patent publication hlo. 0,053;321 [priority: 28th November 1980 (DE 3,044,810), publication date in the German Federal Republic: 9th June 1982 (Patentblatt 82/23)-i herbicidal new phenoxy cinnamic acid derivatives are disclosed. Phenoxy-2-nitro-benzaldehyde derivatives Nos. 1 and 2 and also substituted phenoxybenzaldehvde derivatives Nos. 3 and 4 are mentioned as intermediates of the synthesis but not herbicidal effect is attributed to them.

In European patent publication No. 0,064,658 [priority: 9th May 1981,(DE 31 18 371); publication date in the German Federal Republic 17th November 1982, Patentblatt82j46] new phenoxy benzaldehyde acetals having herbicidal and plant growth regulating effect are disclosed. In the synthesis thereof as example 5-[(2-chloro-4-trifluoromethyl)-phenoxy]-2-nitrobenzaldehyde and 5-[(2,6-dichloro-4-trifluoromethyl)- phenoxy]-2-nitro-benzaldehyde are enumerated but no herbicidal effect is attributed to these compounds (see US patent No. 4,306,900). The said two intermediates are identical with compounds Nos. 1 and 2.

It appears from the said patent specifications that from the four compounds falling under the general Formula I compounds Nos. 1 and 2 (substituted phenoxy-4-nitro-benzaidehydes) possess herbicidal effect but biological data have been disclosed only for compound No. 1.

On carrying out tests with substituted phenoxy benzaldehydes it has been found in a surprising manner that Compounds Nos. 1-4 exhibit fungicidal effect. This recognition is so much the more surprising that on the basis of most recent and uptodate prior art (particularly in the knowledge of US patent No.4,306,900 and DOS No.3,017,795) the skilled art worker could only draw the conclusion that substituted phenoxy benzaldehydes and nitro derivatives thereof possessed herbicidal properties.

In the manual of R. Wegler: "Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel" Vol. 5., Seringer-Verlag Berlin, Heidelberg New York 1977 (pages 7382 and 401-407) "diphenyl ethers" (substituted phenoxy benzene derivatives) are taught to be herbicides applicable in cultures of soya, maize and rice.

The fungicidal compositions of the present invention comprise as active ingredient an effective amount-generally 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 further auxiliary agents.

The known compounds of the general Formula I may be prepared by methods known per se. The preparation of the said active ingredients is shown in the following Examples.

3-[(2,6-dichloro-4-trifluoromethyl)-phenoxy]-benzaldehyde (Compound No. 4) From 6.1 g (0,05 mole) of 3-hydroxy-benzaldehyde and 2.8 g (0.06 mole) of potassium hydroxide in 150 ml of anhydrous methanol under inert atmosphere the potassium salt of 3-hydroxy-benzaldehyde is prepared. From the homogenous solution the methanol is distilled off in water-pump vacuo and to the residue 2.5 g of potassium carbonate, 50 ml of dimethyl sulfoxide and 13,75 g (0.055 mole; a 10% molar excess) of 3,4,5-trichloro-benzotrifluoride are added. The reaction mixture is heated at 14F144 C for 8 hours under stirring, the dimethyl sulfoxide is distilled off, to the residue 150 ml of benzene are added and the suspension is stirred for an hour.The solid material insoluble in benzene is filtered off and the filtrate is evaporated in water-pump vacuo. The residue is crystallized from a 1:1 mixture of methanol and isopropanol. Thus 9 9 of the desired compound are obtained, yield 60%. Mp.: 49--50C.

White crystals.

Brutto Formula: C14H7Cl2F302 Molecular weight: 335 (calculated).

The mass spectrum contains the fragments characteristic of compounds comprising two chlorine atoms.

M/e (r.i.)=336 (580)=F3C(CI)2C6H2OC6H4CHO 335 (370)=F3C(Cl)2C6H2OC6H4CHO 334 (1000)=F3C(CI)2C6H2OC6H4CHO 333 (370)=F3C(CI)2C6H2OC6H4CHO 271 (520)=F3C(CI)C6H2OC6H5 236 (560)=F3CC6H2OC6H5 In the IR spectrum the band appearing at 1690 cm1 is characteristic of the vibration of the vCO of the formyl group.

The 3-[(2-chloro-4-trifluoromethyl)-phenoxy]-benzaldehyde (Compound No.3) is prepared in an analoguous manner.

5-[(2,6-dichloro-4-trifluoromethyl)-phenoxy]-2-nitro-benzaldehyde (Compound No. 2) 3.75 g (0.011 mole) of 3-[(2,6-dich ioro4-trif luoromethyl )-phenoxyl-benzaldehyde are dissolved in a mixture of 8.6 ml of dichloromethane and 5.3 ml of acetic anhydride, whereupon nitrating acid prepared from 2.4 ml (0.034 mole) of 65% nitric acid and 2.4 ml of 98% sulfuric acid is added dropwise under stirring at such a rate that the temperature of the system should not exceed 10 C. After the termination of the addition stirring is continued at room temperature for 3 hours whereupon the dichloro methane is removed in water-pump vacuo and the residue is poured into ice-cold water. The precipitated white powdery substance is filtered off and dried. Thus 2.7 g of the desired compound are obtained in the form of white crystals, yield 64%. Mp.: 117-119.

Brutto Formula C14H6O4Cl2F3 Molecular weight: 379 (calculated).

The mass spectrum of the product indicates at each fragment the isotope ratio characteristic of compounds comprising two chlorine atoms.

m/e (r.i.)=381 (720)=F3C(Cl)2C6H2OC6H3(NO)CHO 379 (1000)=F3CSC1)2CsH2OC6H3(NO)CHO 349 (650)=F3C(Cl)2C6H2OC6H3(O)CHO 285 (320)=F2C(CI)2C6H2OC6H4 230 (220)=F3C(Cl)2C6H2OH Under the effect of internal circular currents the signs of aromatic aldehydes appear at large 6 values; between 9.6 and 10.5 ppm. The aldehyde proton of the starting material is at 9.85 ppm while the nitrated derivative gives a signal under the effect of the inductive effect at 10.35 ppm.

The band appearing at 1690 cm-l in the IV spectrum characteristic of the vCO vibration of the formyl group. The spectroscopical data prove unambiguously that under the conditions of nitration the oxidation of the formyl group into a carboxy group does not take place.

The 5-[(2-chloro-4-trifluoromethyl)-phenoxy]-2-nitro-benzaldehyde is prepared in an anaiogous manner.

The fungicidal compositions of the present invention can be prepared by methods known per se. Thus the compositions of the present invention may be e.g. wettable powders (WP), suspension concentrates (SC), water-miscible solution concentrates (SC), emulsifiable concentrates (EC), ultra-low volume (ULV) compositions or foils, preferably seed-foils. The said compositions can be prepared by admixing the active ingredient(s) with solid or liquid inert carriers, solvents and optionally further auxiliary agents.

The said auxiliary agents may be e.g. surfactants (e.g. wetting, suspensing, dispersing, emulsifying agents, or agents preventing clotting, anti-caking agents, agents which promote adhesion, spreaders, agents enhancing penetration and substances which maintain or improve biological effect, antifoam agents etc.

Suitable solid carriers and diluents are inactive mineral substances (e.g. China-clay, kaolin, porcelain earth, attapulgite, montmorrilonite, mica slate, pyrophilite, bentonite, diatomaceous earth, highly dispersed synthetic silicic acids, calcium carbonate, calcinated magnesium oxide, dolomite, gypsum, tricalcium phosphate, Fuller's earth etc.). Further suitable solid carriers and diluents are ground tobacco stem, wood-flour etc.

Suitable liquid carriers, diluents and solvents are the followings: water, organic solvents, mixtures of water and organic solvents, e.g. methanol, ethanol, n- or isopropanol, diacetone alcohol, benzyl alcohol, glycols such as ethylene glycol, triethylene glycol and propylene glycol; esters of the above compounds, e.g. methyl cellosolve, butyl diglycol; ketones e.g. dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone etc; esters e.g. ethyl acetate, n- and isobutyl acetate, amyl acetate, isopropyl miristate, dioctyl phthalate, dihexyl phthalate etc; aromatic aliphatic, alicyclic hydrocarbons, such as paraffine hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetraline, decaline, mixtures of alkyl benzenes; chlorinated hydrocarbons e.g. trichloro ethane, dichloro methane, perchloro ethylene, dichloropropane, chloro benzene etc, lactones e.g.y-butyrolactone etc; lactams e.g. N-methyl pyrrolidone, N-cyclohexyl pyrrolidone; acid amides e.g. dimethyl formamide etc; oils of vegetable or animal origin e.g. sunflower-seed oil, flax-seed oil, rape-seed oil, olive-oil, soya oii, castor oil and sperm oil etc.

Suitable wetting, dispersing and emulsifying agents and also adhesion increasing and aggregation preventing agents and spreaders may be of an ionic or non-ionic character.

The ionic agents may be e.g. salts of various saturated or unsaturated carboxylic acids; sulfonates of aliphatic, aromatic or aliphatic-aromatic hydrocarbons; sulfates of alkyl, aryl and aralkyl alcohols; sulfonates of alkyl, aryl and aralkyl acids, esters and ethers; sulfonates of condensation products of phenol, cresol and naphthalene; sulfonated oils of vegetable or animal origin; alkyl, aryl and aralkyl phosphate esters; and salts of the above compounds formed with alkali or alkaline earth metals or organic bases (e.g.

salts formed with amines or alkanol amines). Preferable examples of the said ionic surfactants are the following compounds: sodium lauryl sulfate, sodium-2-ethyl-hexyl sulfate; the sodium, ethanol amine, diethanol amine, triethanol amine and isopropyl amine salt of dodecyl benzene sulfonic acid; sodium mono- and diisopropyl naphthalene sulfonate; sodium salt of naphthalene sulfonic acid sodium diisooctyl sulfosuccinate; sodium xylene sulfonate; sodium and calcium salt of petroleum sulfonic acid, potash soaps, potassium, sodium, calcium, aluminium and magnesium stearate etc. The phosphate esters may be ethers of phosphated alkyl phenols or fatty alcohols formed with polyglycol and forms of the above compounds partially or completely neutralized by the above cations or organic bases.Further suitable anionic surfactants are the disodium N-octadecyl-sulfosuccinate, sodium-N-oleyl-N-methyl-tauride and various ligno-sulfonates.

Suitable non-ionic wetting, dispersing and emulsifying agents are ethers of ethylene oxide formed with C10~20 alcohols, such as stearyl-polyoxy ethylene, oleyl polyoxy ethylene ethers formed with alkyl phenols e.g. polyglycol ethers formed with tertiary butyl phenol, octyl phenol or nonyl phenol; esters formed with organic acids e.g. esters of stearic acid or miristic aid 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 e.g. esters of sorbitol formed with oleic acid or stearic acid; condensation products of such compounds formed with ethylene oxide; tertiary glycols e.g. 3,6-dimethyl-4octine-3,6-diol or 4,7-dimethyl-5-decine-4,7-diol; thioethers of polyethylene glycol e.g. ethers of dodecyi mercaptane formed with polyethylene glycol etc.

Suitable adhesion improving agents are the alkaline earth metal soaps; salts of sulfosuccinic acid esters; natural and artificial water-soluble macromolecules, e.g. caseine, starch vegetable gums, Arabian gum, cellulose ethers, methyl cellulose, hydroxy ethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol etc. Suitable antifoaming agents are polyoxy ethylene or polyoxy propylene block polymers of low molecular weight (in which the number of octyl, nonyl and phenyl-polyoxy ethylene/ethylene oxide units is A5); long chained alcohols e.g. octyl alcohol etc; special silicon oils, etc.

Suitable additives may also be added in order to make the formulated compositions compatible in colioidal-chemical respect with various fertilizers systems.

The fungicidal compositions of the present invention may also comprise known pesticides and/or nutrient components.

The wettable powders (WP) may be prepared by admixing the active ingredient(s), auxiliary agent(s) and surfactant(s) with the carriers and grinding and finally homogenizing the mixture. If liquid surfactants are used one may also proceed by applying the liquid surfactant onto the solid organic or inorganic carrier(s) or onto the powder mixture comprising the solid active ingredient(s) by spraying. This method is also applicable for liquid active ingredients.

If liquid surfactants are used one may also proceed by suspending the previously ground solid components in an organic solvent which contains the liquid surfactant(s). The suspension thus obtained may be dried e.g. by spraying. Thus the surfactant is applied onto the surface of the solid active ingredient or solid carrier.

An emulsifiable concentrate (EC) may be prepared by dissolving the active ingredient or a mixture thereof in the presence of an above surfactant in a water-nonmiscible solvent. The emulsifiable concentrate thus obtained forms with water spontaneously or under using a small mechanical effect a ready-for-use spray which remains unchanged even after long storing. A water-miscible solution concentrate (SL) can be prepared by dissolving the active ingredient in water and/or a water-miscible solvent in the presence of a suitable water-soluble auxiliary agent. On diluting with water a spray having the desired concentration can be obtained.

The aqueous solution concentrates of the active ingredient can also be dispersed in water-nonmiscible solvents by proper selection of the emulsifier; thus so-called invert emulsions are obtained. Thus by proper selection of the solvent and surfactants compositions can be prepared which on admixture with water or water-nonmiscible liquids form dispersed-sometimes molecularly dispersed-systems which remain unchanged for a longer period of time.

Suspension concentrates (SC) are prepared by dissolving the wetting and dispersing agents in a mixture of water (preferably ion-exchanged) and an anti-freezing component (preferably ethylene glycol or glycerol) if necessary under heating. To the solution thus obtained the solid (powdered or crystalline) active ingredient(s) and if necessary the anti-caking-component (e.g. Aerosil 200) is (are) added under constant stirring. The particle-liquid phase system thus obtained (slurry) is ground in a wet grinding apparatus (e.g. a closed Dyno mill) to the desired particle size, preferably not larger than 5 micrometers in order to provide suitable storing stability. After grinding an antifoam agent or a thickening component (e.g. Kelzan S) is added under homogenization, if desired.One may also proceed by changing or modifying the order of the addition of the components or by adding further components (e.g. dyes) if necessary. In addition to the solid active ingredient as combination partners liquid water-immiscible or water-miscible active ingredients may also be used. Active ingredients having a low melting point may be added as a melt in the presence or absence of an emulsifier.

The ULV compositions can be prepared in a simular manner to the EC compositions and in certain cases to the SC forms.

Granules suitable for direct use (G) may be prepared by extrusion, or lamination by using a granular carrier (e.g. ground limestone) or absorbing the liquid component by a carrier having an absorbing capacity.

Granules suitable for atomizing (WG) can be prepared starting from a WP and/or SC form with the aid of an agglomeration technology (e.g. in a dragee pan by using a binder).

The active ingredient content of the fungicidal compositions of the present invention is generally 0.000199% by weight, preferably 0.0195% by weight.

The ready-for-use sprays and dusting powders can be prepared from the above compositions by diluting with water or an inert solid diluent in a known manner. The active ingredient content of the ready-for-use compositions is generally 0.000110% by weight, preferably 0.015% by weight. One may also proceed by admixing before use the sprays prepared from several compositions each containing one active ingredient.

Seed-foils are a preferred embodiment of the compositions of the present invention. Seed-grain foils are prepared by incorporating the active ingredient either into the foil or into the seed-grains.

According to further feature of the present invention there is provided a method for combating fungal diseases in plants which comprises applying an effective amount of at least one compound of the general Formula I onto the plants, orfungal pests or environment thereof.

The composition of the main types of the fungicidal agents of the present invention is disclosed below.

The amounts are to be understood in % by weight.

Suspension Concentrate (SC) Compound No. 4 40.0% Ethylene glycol 10.0% Nonyl phenyl polyglycol ether (10 EO) 5.0% Polysaccharide (xanthane gum) 0.1% Silicon oil 1.0% Water 43.9% Wettable Powder (WP) Compound No. 1 30.0% Highly dispersed silicic acid 15.0% China-clay 20.0% Sodium lignosulfonate 5.0% Diatomaceous earth 25.0% Dispersing agent 5.0 /O Granules (G) Compound No. 3 5.0% Ground limestone 69.0% Ethylene glycol 3.0% Calcium lignosulfonate 3.0% Highly dispersed silicic acid 5.0% Water 15.0% Dry Flowable Granule Suitable for Spraying (WG) Compound No. 4 80.0% Mixture of anionic and non-ionic emulsifiers 2.0% Dispersing agent 7.0% China clay 8.0% Water 3.0% Emulsifiable Concentrate (EC) Compound No. 2. 20.0% Xylene 50.0 MO Cyclohexanone 12.0% Isophorone 10.0% Poly(oxyethylene)sorbitol monooleate 5.0% Sodium lignosulfonate 3.0% Seed-foil a) Preparation of the Foil 80 g of RHODOVIOL 4/125 P type polyvinyl alcohol (the viscosity of a 4% aqueous solution amounts to 4 cP at 20"C; hydrolysed by 89 molar %) are added to 615 g of water (60"C) under stirring. After dissolving 20 g of RHODOVIOL 30/20 m type polyvinyl alcohol (the viscosity of a 4% aqueous solution amounts to 30 cP at 20"C; hydrolysed by 98 molar %) and 20 g of glycerol are added to the solution and the mixture is vigorously stirred until a homogenous solution is obtained. The solution is allowed to stand for 24 hours whereby the bubbles leave the solution.The solution is spread on a glass plate in a layer having a thickness of 0.50 mm by the stripping blade method and dried at room temperature. The foil thus obtained comes unstuck from the glass plate; thickness 0.050.06 mm. (Control foil).

b) Preparation of a Foil Comprising the Active Ingredient One proceeds according to paragraph a) except that to the solution used for the casting of the foil 0.120 g of compound No.2 suspended in 5 ml of water is added. After the removal of the bubbles a foil is cast which is dried. The foil thus obtained is similarto that according to paragraph a) but comprises 1000 ppm of compound No. 2 as active ingredient As active ingredient in the place of compound No. 2. a suspension of 0.0120 g of Compound No. 4 and 5 ml of water can also be used.

The active ingredient content of the foil amounts to 100 ppm.

Seed-dressing, spraying and dusting are the most widespread methods in the combating and control of fungal diseases by chemical plant protection. The composition comprising the fungicidal active ingredient is preferably applied onto a part or the environment of the host plant effected or endangered by the infection.

Seed-dressing may be used for the preparation of seed-grains free of infection and to combate soil fungi which infect the seed-grains. Seed-grains and seedlings are endangered in the first place by mould conidium fungi (e.g. Fusarium graminearum and Fusarium moniliforme and Nigrospora cryzae in maize culture and strains belonging to the Rhizoctonia, Penicillium and Helminthiosporum genus).

Plant stand may be protected against fungal infections endangering the foliage and crop (fruits) of the plants e.g. by spraying or dusting. As fungal diseases e.g. Monilia fructigena and Spilocea pomi (Fusicladium dendriticum) on apple or Botrytis cinerea on grapes can be mentioned.

The fungicidal compositions of the present invention may be used e.g. against the following fungi: a) Moniliaceae Family Genus: Species: Monilia (e.g. M. fructigena) Aspergillus (e.g. A. niger) Penicillium (e.g. P. crustaceum) Botrytis (e.g. B. cinerea) Verticillium (e.g. V. albo-atrum) Trichothecium (e.g. T. roseum) Cercosporella (e.g. C. herpotrichoides) b) Dematiaceae Family: Genus: Strain: Thielaviopsis (e.g. T. basicola) Nigrospora (e.g. N. oryzae) Spilocea (e.g. S. pomi, szinonim Fusicladium dendriticum) Cladosporium (e.g. C. fulvum) Helminthosporium (e.g. H. turcicum) Cercospora (e.g. C. beticola) Alternaria (e.g. A. solani) Stemphylium (e.g. S. radicinum) c) Tuberculariaceae Family: Genus: Strain: Fusarium (e.g.F. graminearum and F. oxysporum In the following activity examples the effect of the compositions of the present invention is compared to that of 1 ,2,5,6-tetrahydro-N-(trichloromethylth io)-phthal imide (Captan), a known fungicide.

EXAMPLE 1 Testing of Fungicidal Activity An agarplate is prepared by casting a potato agar nutrient medium containing 2% of dextrose into a Petri plate (diameter 100 mm) and allowing 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 test fungi is prepared in such a dilution that when 1 drop of the spore suspension is placed on the glass slide of the microscope at a 10Q160 fold magnifying 2530 spores should appear on the visual field, on the basis of the average of 5--10 visual fields.

From the spore suspensions thus obtained 1 ml is pipetted to 1 ml of the solution of the active ingredient, the mixture is allowed to stand for 30 minutes and applied onto the agar plate. The fungi are inoculated until vigorous growth begins, whereupon the results are evaluated by comparing the growth of the treated samples to that of the control on the basis of the following scale: 1 = no growth of the colonies (0% related to the control) 2=weak growth of the colonies (10% related to the control) 3= medium growth of the colonies (50% related to the control) 4=strong growth of the colonies (100% related to the control).

The results are summarized in Table 1.

TABLE 1 Fungicidal Activity Against Aspergillus Niger (A) and Botrytis Cinerea (B) Concentration Colony Growth in Value Numbers of Active Replicates Colony Growth, Fungicidal Activity, Compound Ingredient, (A) (B) Average % % No. ppm 1 2 3 4 Average 1 2 3 4 Average (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 10 10 90 90 80 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 1 1 0 0 100 100 2000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 2 400 2 3 2 3 2.5 2 2 2 2 2 30 10 70 90 80 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 2 3 2 3 2.5 10 30 90 70 2000 3 3 3 3 3 3 3 3 3 3 50 50 50 50 3 400 4 4 4 4 4 4 4 4 4 4 100 100 0 0 80 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 TABLE 1 (cont.).

Fungicidal Activity Against Aspergillus Niger (A) and Botrytis Cinerea (B) Concentration Colony Growth in Value Numbers of Active Replicates Colony Growth, Fungicidal Activity, Compound Ingredient, (A) (B) Average % % No. ppm 1 2 3 4 Average 1 2 3 4 Average (A) (B) (A) (B) 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 4 100 100 0 0 80 4 4 4 4 4 4 4 4 4 4 100 100 0 0 16 4 4 4 4 4 4 4 4 4 4 100 100 0 0 10000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 Captan 2000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 standard 400 2 2 2 2 2 2 2 2 2 2 10 10 90 90 80 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 #Control - 4 4 4 4 4 4 4 4 4 4 100 100 0 0 EXAMPLE 2 Fungitoxical Test in Liquid Culture The active ingredient is emulsified in 20 ml of a 2% malt nutrient medium in the desired concentration, whereupon the nutrient medium is inoculated with the test fungus. The rate of inhibition of the growth of the colonies is determined after an incubation period of 7 days. The concentrations required for complete growth inhibition are disclosed in Table 2.

TABLE 2 Fungitoxical Effect Concentrations in ppm Captan No of Active Ingredient Genus Standard 1 2 3 4 Fusariumoxysporum 300 300 300 1000 1000 Fusarium nivale 300 300 300 1000 1000 Fusariumsolani 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 100-300 100-300 100-300 1000 300 Cercospora beticola 100-300 100-300 100-300 1000 300 Stemphylium radicinum 100-300 100-300 100-300 1000 300 Trithothecium roseum 100-300 100-300 30-100 300 300 Thielaviopsis basicola 100-300 30-100 30-100 100-300 100-300 Nigrospora oryzae 30-100 30-100 30-100 100-300 100-300 Cladosporium cucumerinum 30-100 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 Manilia fructigena 30 30 30 100-300 100-300 EXAMPLE 3 Testing of Phytotoxicity in Glass-house Growth plates havirig a surface of 1.64 dm2 are filled with sand soil and 20 or 30 seeds (depending on the test plant) are sown in two replicates into 0.5-1.0cm deep drills. 10 days after the shooting of the plants ready-for-use sprays prepared from a 20% emulsifiable concentrate of the active ingredient are applied onto the seedlings at a concentration corresponding to a dose of 1,3 and 9 kg of active ingredient/ha, respectively, with the aid of a laboratory sprayer. The percental damages of the plants are determined 10 days after spraying.The results are summarized in Table 3.

The following test plants are used: A=soya (Glycine soja) B=Autumn wheat (Triticum aestivum) C=Autumn barley (Hordeum vulgare) D=Maize (Zea mays) E=ltalian millet (Setaria italica) F=Cotton (Gossypium hirsutum) G=White mustard (Sinapis alba) H=Bean (Phaseolus vulgaris) I=Pea (Pisum sativum) K=Lupine (Lupinus albus) L=Broad-bean (Vicia faba) M=Medic (Medicago sativa) N=Carrot (Daucus carota) O=Sugar beat (Beta vulgaris) P=Sunflower (Heiianthus annuus) TABLE 3 Phytotoxicity Tests Active Ingredient Compound No.

1 2 3 4 Plant Dose (kg ha-1) Species - Untreated Tested 1 3 9 1 3 9 1 3 9 1 3 9 Control A 0 5 10 0 5 15 0 0 10 0 0 15 0 B 5 10 30 0 10 30 0 0 20 0 5 25 0 C 10 35 50 15 25 50 10 20 40 10 20 40 0 D 10 40 60 30 50 70 15 20 45 20 30 50 0 E 60 80 100 50 75 100 30 60 100 30 70 100 0 F 80 95 98 30 65 90 30 40 70 30 50 75 0 G 40 60 90 50 80 95 30 50 100 35 60 95 0 H 50 80 80 45 65 85 0 10 50 5 15 40 0 I 15 30 50 10 40 60 10 30 40 20 30 40 0 K 40 50 70 50 60 70 10 15 20 10 20 25 0 L 70 80 90 80 90 100 25 50 75 20 35 55 0 M 60 90 100 70 80 95 30 50 90 30 60 95 0 N 10 20 70 30 70 90 30 50 80 20 40 65 0 0 10 10 20 15 25 30 20 40 60 25 50 75 0 P 40 50 75 10 35 60 20 40 80 30 50 75 0 EXAMPLE 4 Protection Against Fungal Diseases of Soyabean by Seed-dressing Seed-dressing is carried out by using a 400 g/l suspension concentrate of the active ingredient and a 50% WP form of Captan as standard, respectively 0.1; 0.25; 0.5; 1.0 and 2.0 g/kg of active ingredient are applied onto the surface of seed-grains of the Merit soya type. Percental germination and fungal infection are determined in a laboratory 10 days after seed-dressing.

In field experiments plots are sown on the 20th April (deepness: 4--5 cm); stem distance: 5 cm; row distance: 50 cm. When the stand height of the soya reaches 10-12cm, the shooted plants are counted and expressed as the percentage of the untreated control. The results are summarized in Table 4.

TABLE 4 Soya Seed-dressing Test Dose of No. of Active Infection % of Seed-grains Germination No. of Plants Active Ingredient Alternaria Penicillium Fusarium %, in on Field, as % of Ingredient g/kg sp. sp. sp. Laboratory Control 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 96 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 0.1 26.4 3.2 3.0 82 102 0.25 13.6 2.2 1.5 90 116 Captan 0.5 7.5 0.2 0.5 94 121 standard 1 2.6 - - 90 114 2 0.8 - - 90 105 q) Control - 75.0 12.0 6.0 78 100 EXAMPLE 5 Protection Against Fusariosis of Ear of Autumn Wheat The tests are carried out on plots (10 m2) on Autumn wheat (Jubilejnaja) in four replicates. From 20% emulsion concentrates of compounds Nos. 1--4 ready-for-use sprays are prepared and spraying is carried out at the end of earing at a dose of 1, 2 and 3 kg of active ingredient/ha, respectively, at a watering rate of 5001 of water/ha. Fusarium infection of the ears is determined 12 days after spraying by evaluating 200 ears/plot. The crop of each plot is weighed after harvesting and the total and internal Fusarium infection of the seeds is determined on the basis of an average sample of 200 seeds/plot The results are summarized in Table 5 and expressed as the average of four replicates.

TABLE 5 No. of Infection % of Fusarium spp.

Active Dose Seed Seed Crop Weight Ingredient kg/ha Ears Total Internal [kg/10 m2] 1 0.86 12.2 8.8 5.67 1 2 0.54 9.6 7.6 5.88 3 0.48 5.4 4.4 6.03 1 0.63 13.4 10.2 6.11 2 2 0.33 10.2 8.1 5.87 3 0.20 6.0 5.4 5.84 1 1.09 11.4 9.4 5.62 3 2 0.84 10.6 8.0 5.66 3 0.67 9.8 7.2 5.73 1 0.98 9.9 6.8 5.78 4 2 0.68 9.2 6.4 5.82 3 0.52 8.0 6.1 5.87 Untreated 0 10.80 35.45 30.25 4.84 control

Claims

1. Fungicidal composition comprising as active ingredient in an effective amount at least one phenoxy benzaldehyde derivative of the general formula I

(wherein X stands for hydrogen or chloine and Y represents hydrogen or nitro) in admixture with at least one auxiliary agent or diluent.

2. Fungicidal composition according to Claim 1 comprising as active ingredient 3-[(2-chloro-4trifluoromethyl)-phenoxy]-benzaldehyde.

3. Fungicidal composition according to Claim 1 comprising as active ingredient 3-[(2,6-di-chloro-4trifluoro-methyl)-phenoxy]-benzaldehyde.

4. Fungicidal composition according to Claim 1 comprising as active ingredient 5-[(2-chloro-4- trifluoromethyl)-phenoxyj-2-nitro-benzaldehyde.

5. Fungicidal composition according to Claim 1 comprising as active ingredient 5-[(2,6-dichloro-4 trifluoromethyl )-phenoxy]-2-nitro-benzaldehyde.

6. Process for combating fungal diseases of plants which comprises applying at least one compound of the general Formula I (wherein X stands for hydrogen or chlorine and Y represents hydrogen or nitro) in an effective amount onto the plants or the growing space or environment thereof.

7. Use of phenoxy benzaldehyde derivatives of the general Formula I (wherein X stands for hydrogen or chlorine and Y represents hydrogen or nitro) again for the protection of plants against fungal diseases.

8. A fungicidal composition as claimed in claim 1 substantially as hereinbefore described.

9. A process as claimed in claim 6, substantially as hereinbefore described.