GB2154235A - Fungicidally active phenoxy benzaldehyde derivatives - Google Patents

Abstract

The invention provides compounds of formula I <IMAGE> wherein R1 and R3 stand for trifluoromethyl or nitro with the proviso that R1 and R3 are different; R2 is hydrogen or 3-formyl-phenoxy: X represents hydrogen or chlorine and Y stands for hydrogen or nitro/ and fungicidal compositions comprising the same. These compounds can be prepared by reacting 3-hydroxy-benzaldehyde or an alkali metal salt thereof with a compound of Formula II <IMAGE> and if desired nitrating the compound of Formula I/a <IMAGE> thus obtained into the corresponding compound of Formula I/b <IMAGE>

Description

SPECIFICATION Phenoxy benzaldehyde derivatives This invention relates to new phenoxy benzaldehyde derivatives, a process for the preparation thereof, fungicidal compositions containing the same and a method for combating fungal diseases of plants.

Substituted phenoxy benzene derivatives /according to previous nomenclature: diphenyl ethers/ have become known about twenty years ago as herbicides particularly useful in rice, cotton and soyabean cultures. This compound group is described in details in the manual of R. Wegler: "Chemie der Pflanzenschutzund Schädlingsbekämpfungsmittel" Vol. 5/Springer Verlag Berlin-Heidelberg-New York 1977), pages 73-80 and 401-407.The following diphenyl ether derivatives possess particularly strong herbicidal properties: 2-nitro-1 44-nitro-phenoxy/-4-trifluoromethyl-benzene /Fluorodiphen/; 2-chloro-1-/ nitro-phenoxy/-4-trifluoromethyl-benzene /Nitrofluorophen/; 2-chloro-1-/3-ethoxy-4-nitro-phenoxy/-4- trifluoromethyl-benzene lOxyfluorophen!; sodium-542-chlorn-4-trifiuornmethyl-phenoxW-2-nitro-benzoate lacylfluorophen sodium/ and ethyl-5-/2-chloro-4-trifluoromethyl-phenoxy/-2-nitro-benzoate lacylfluorophen ethyl.

- see US Patent specifications Nos 3,798,276, 4,031,131,4,1 64,408, British patent specification No.

1,390.295 and DOS No. 2,333,848.

The chemically most closely related but structurally still different compounds to the phenoxy benzaldehyde derivatives of the present invention are disclosed as herbicides in US patent specification No.

4,306,900 and DOS No.3,017,795. The fungicidal effect of these known compounds is described in our copending application that claims priority from Hungarian Patent Application Serial No. 157/84. The activity of the known compounds is however not always satisfactory.

The object of the present invention is to provide new phenoxy benzaldehyde derivatives having high fungicidal activity.

It has been found that the new phenoxy benzaldehyde derivatives are excellent fungicides.

According to a feature of the present invention there are provided new phenoxy benzaldehyde derivatives of the general Formula I

wherein R1 and Rg stand for trifluoromethyl or nitro with the proviso that R1 and R3 are different; R2 is hydrogen or 3-formyl-phenoxy; X represents hydrogen or chlorine and Y stands for hydrogen or nitro.

According a further feature of the present invention there are provided fungicidal compositions comprising in an effective amount at least one compound of the general Formula I/wherein F1, R2, F3, X and Y are as stated above/ in admixture with at least one inert carrier, diluent and/or auxiliary agent.

According to a still further feature of the present invention there is provided a process for the preparation of compounds of the general Formula I/wherein R1, R2, F2, X and Y are as stated above/ which comprises reacting 3-hydroxy-benzaldehyde or an alkali metal salt thereof in the presence of an inert diluent with a substituted benzene derivative of the general Formula II

/wherein R1, R2, R3, X and Y are as stated above and Hal represents halogen, preferably chlorine/, isolating the phenoxy benzaldehyde derivative of the general Formula I/a (I/a)

thus obtained from the reaction mixture !wherein R1, R2, R2, X and Y are as stated above/, if desired nitrating the compound of the general Formula I/a and isolating the compound of the general Formula l/b

thus obtained from the reaction mixture /wherein R1, R2, R3, X and Y are as stated above/.

According to the process of the present invention the new compounds of the general Formula I are prepared by reacting 3-hydroxy-benzaldehyde or an alkali metal salt- preferably sodium or potassium saltthereof in the presence of an inert solvent with a substituted benzene halogenide of the general Formula II, preferably with a substituted chloro benzene of the general Formula II. The 3-hydroxy-benzaldehyde and the compounds of the general Formula II used as starting material are known compounds. The reaction is preferably carried out in the presence of an acid binding agent/e.g. alkali carbonates, such as sodium or potassium carbonate; alkali hydrogen carbonates such as sodium or potassium hydrogen carbonate; or inert alkaline earth metal oxides e.g. magnesium oxide/.Other acid binding agents/e.g. alkali metal alcoholates such as sodium methylate/ may be used as well. As reaction medium any suitable inert organic solvent can be used. The solvent must comply with the following two requirements: al the boiling point of the solvent should not exceed 150 C because too highly boiling solvents can not be easily removed; b/ certain solvents accelerate the reaction velocity and therefor it is preferred to use aprotic solvents.

Particularly do polar aprotic solvents e.g. dimethyl formamide, dimethyl acetamide, sulfolane, dimethyl sulfoxide or acetone.

The reaction can be carried out at room temperature or at on elevated temperature. It is preferred to work at 20-120 C, particularly at 25-100 "C.

The reaction period is between some hours and a day, depending on the reaction temperature used.

The reaction product can be isolated from the reaction mixture by methods known per se, e.g. filtration, evaporation of the solvent, washing of the moist product, drying etc.

The 5-isubstituted phenoxy2-nitro-derivatives of the general Formula l/b can be preferably prepared by direct nitration of the 3-/substituted phenoxyl-benzaldehyde derivatives of the general Formula lia. Nitration is carried out by methods known per se. One may work preferably by nitrating the compound of the general Formula I/a in an inert organic solvent /e.g. chlorinated hydrocarbons, particularly dichloro methane, dichloro ethane etc./ in the presence of acetic anhydride with nitrating acid at a lower temperature.

The reaction mixture is poured on ice or into water, the precipitated product is separated and if desired purified by known methods/e.g. recrystallization etc./.

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 IWPI, suspension concentrates/SC/, water-miscible solution concentrates ISCI, emulsifiable concentrates IECI, ultra-low volume IULVI compositions or foils, preferably seedfoils. The said compositions can be prepared by admixing the active ingredientisiwith 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 le.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 following: 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 paraffin hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetraline, decalin, mixtures of alkyl benzenes; chlorinated hydrocarbons e.g. trichloro ethane, dichloro methane, perchloro ethylene, dichloro propane, chloro benzene etc, lactones e.g. -butirolactone etc; lactams e.g. N-methyl pyrrolidone, N-cyclohexl 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 oil, castor oil and sperm oil etc.

Suitable wetting, dispersing and emulsying 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 lignosulfonates.

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-4-octine-3,6-diol or4,7-dimethyl-5-decine-4,7-diol; thioethers of polyethylene glycol e.g. ethers of dodecyl 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. casein, starch, vegetable gums, Arabic 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 > 5/; 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 colloidal-chemical respect with various fertilizers systems.

The fungicidal compositions of the present invention may also comprise known pesticides andíor nutrient components.

The wettable powders /WP/ may be prepared by admixing the active ingredient/s/, auxiliary agent, 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-non miscible 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 /scurry/ 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 two 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 IWGI 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 0.0001-99% by weight, preferably 0.01 -95 % 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 0.0001-10 % by weight, preferably 0.01-5 % by weight. One may also proceeed 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 a further feature of the present invention there is provided a method for combating fungal diseases of plants which comprises applying an effective amount of at least one compound of the general Formula I onto the plants or fungal pests or environment thereof.

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 oryzae 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: al 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/ Thielaviopsis /e.g. T. basicola/ Nigrospora :e.g. N. oryzae/ Spilocea /e.g. S. pomi szinonim Fusicladium dendriticum/ Cladosporium /e.g. C. fulvumI Helminthosporium /e.g. H. turcicum/ Cercospora /e.g. C. beticola/ Alternaria /e.g. A. solani/ Stemphylium /e.g. S. radicinum/ cl Tuberculariaceae family Genus: Species: Fusarium /e.g.F. graminearum and F. oxysporuml Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples.

II Preparation of the active ingredients EXAMPLE 1 3-[/5-chloro-4-trfflurom eth yl-2-nitro/-ph en oxy]-h enzaldeh yde / Compound No. 11 7.8 g /0.03 mole/ of 2,4-dichloro-5-nitro-benzotrifluoride, 4.4 g /0.036 mole; a 20 % molar excess of 3-hydroxy-benzaldehyde and 4.97 g /0.036 mole/ of an hydrous potassium carbonate are added to 50 ml of anhydrous acetone and the suspension is stirred at room temperature for 16 hours. The reaction mixture is filtered and the filtrate is evaporated in water-pump vacuo. The oily residue is dissolved in boiling isopropanol and the solution is slowly cooled under stirring. Thus 8.0 g of the desired compound are obtained, yield 77 %, mp.: 80-83 C. Beige crystals.Brutto formula: C,4H704NCIF3, molecular weight: 345 /calculated/ The mass spectrum contains the following characteristic fragments: m/e /r.i./ = 345 /800/ = F3C/CI//NO2/C6H2OC6H4CHO 300 /300/ = F3C/CI/C6H3OC6H4CHO 328 /150/ = F3C/CI//NO2/C6H2OC6H4C 224 /1000/ = F3C/CIflNO2/C5H2 121 /620/ = OC6H4CHO On the 1H-NMR spectrum the assignation of the protons to the corresponding sign is complicated because of the overlapping of the different signs. The formyl proton of the coupled compound appears at 9.92 ppm.

In the IR spectrum the wCO band of the formyl group appears at 1680 cm- and the WCH band of the formyl group appears at 2830 and 2730 cm-'.

EXAMPLE 2 3-/4-trifluoromethy1-2, 6-dinifrol-phenoxy]-benzaldehyde ICompound No. 2/ One proceeds according to Example 1 except that in the place of 2,4-dichloro-5-nitro-benzotrifluoride 3,5-dinitro-4-chloro-benzotrifluoride is used as starting material. Thus 9.5 of the desired compound are obtained in the form of yellow crystals. Yield 80 %. Mp.: 130-131 C. Brutto Formula : Ca4H706N2F3, molecular weight 346 Icalculatedl.

The mass spectrum contains the following characteristic fragments: mle /r.i./ = 356 /870/ = F3C/NO2/2C6H2OC6H4CHO 337 /1001 = F2C/NO2/2C6H2OC6H4CHO 235 /180/ = F3C/NO2/2C6H2 121 /10001 = OC6H4CHO On the 1H-NMR spectrum the two protons between the trifluoromethyl and nitro group appears at 8.42 ppm and the formyl proton appears in an intensity ratio corresponding to 9.85 ppm.

In the IR spectrum the vibrations of the yCO 11685 cm-1/ and the wCH vibrations /2830 and 2940 cm-1/ of theformyl group can be identified unambiguously.

EXAMPLE 3 3-[i2-trifluoromethyl-4, 6-dinitrol-phenoxy]-benzaldehyde compound No. 3/ One proceeds according to Example 2 except that in the place of 2,4-dichloro-5-nitro-benzotrifluoride 2-chloro-3,5-dinitro-benzotrifluoride is used as starting material. Thus 8.1 of the desired compound are obtained in the form of light yellow crystals. Yield 76 %.

Mp.: 104 C.

Brutto formula: Ca4H706N2F3, molecular weight: 356Icalculatedl.

The mass spectrum contains the following characteristic fragments: mle /r.i./ = 356 /880/ = F3C/NO2/2C6H2OC5H4CHO 235 /570/ = F3C/NO2/C6H2 121 /1000/ = OC6H4CHO On the 1H-NMR spectrum the sign of the protons between the trifluoromethyl and the nitro group and that of the protons between the nitro group appear at the expected chemical shift values with a well-recognizable metacoupling. The value of the formyl proton /9.85/us in conformity with the afforesaid.

In the IR spectrum the yCO band of the formyl group appears at 1695 cm-' and the SyCH band of the formyl group at 2750 and 2855 cm-1.

EXAMPLE 4 2,4-bis-/3-formyl-phenoxyl-1-trifluoromethyl-3,5-dinitro-benzene /Compound No. 4/ 3.66 g /0.03 moles of 3-hydroxy-benzaldehyde, 5.06 g 0.017 mole; at 10 % molar excess/ of 2,4-dichloro-3,5-dinitro-benzotrifluoride and 4.55 g 1'0.033 mole; a 10 % molar excess of anhydrous potassium carbonate are added to 50 ml of anhydrous acetone. The reaction mixture is stirred at room temperature for 6 hours and allowed to stand for a day. The suspension is filtered, the precipitate is washed with acetone and the filtrate is evaporated in water-pump vacuo. The residue is dissolved in 60 ml of hot isopropanol and the solution is slowly cooled. Thus 5.3 g of the desired compound are obtained in the form of light yellow crystals, yield 85 %.

Mp.: 137-138 C.

Brutto formula: C21H11O8N2F3, molecular weight 476 calculated/ On the mass spectrum only the double coupled compound can be identified.

m/e /r.i./ = 476 /560/ = F3C/NO2/2C6H4iCHO!2 459 /1000/ = F2C/NO2i2C6H/OC6H4CHO/OCaH4C 367 /220/ = F3CC6H 0C6H4CHO/OC6H40 121 /320' = OC6H4CHO 93 /560/ = OC6H4 On the 1H-NMR spectrum the intensity ratio of the formal proton /9.87 ppm/ and the proton between the trifluoromethyl and nitro group also indicates the presence of the double coupled derivative.

On the IR spectrum the -yCO band of the formyl group appears at 1700 cm-' and the yCH band of the formyl group at 2740,2820 and 2860 cm-1.

EXAMPLE 5 5-[14-trifluoromethyl-2,6-dinitrol-phenoxyl-2-nitro-benzaldehyde Compound No. 5/ 6.05 g /0.07 moles of 3-[/4-trifluoromethyl-2,6-dinitro/ phenoxy ]-benzaldehyde /prepared according to Example 2/ are dissolved in a mixture of 12.5 ml of dichioro methane and 7.6 g of acetic anhydride, the solution is cooled to 10 C and nitrating acid [a mixture cf .8 ml 0.027 mole of 65 O nitric acid and 1.8 ml of 98 % sulfuric acid] is slowly added dropwise. The addition having been completed the reaction mixture is allowed to warm to room temperature.The reaction mixture is stirred for a further period of 3 hours, whereupon the dichloro methane is removed in water-pump vacuo and the residue is poured into 200 ml of icecold water. The precipitated product is filtered off and dried. The product is recrystallized from isopropanol. Thus 4.1 g of the desired compound are obtained in the form of yellow crystals, yield 60 %. Mp.: 129-130 "C.

Brutto formula : C14H6O8N2F3; molecular weight 401 1calculated/.

The mass spectrum contains the following charactensticfragments: m/e/r.i./ = 401 /180' = F3C/NO2/2C6H2OC6H!NO2/CHO 382 /130/ = F3C/NO2/2C6H2OC6H4/NO2iCHO 235 /4001 = F3C/NO2,2C6H2 166 /1000/ = OC6U3/NO2íCHO The fragment of the mass of 166 indicates unambiguously that nitration has been completed. The formyl proton is shifted from 9.85 ppm to 10.255 ppm.

On the IR spectrum the yCO is absorbed at 1700 cm -1, while the bands appearing in the wave number interval of 1520-1550 cm-l are the vibrations of the nitro groups. The NO2 band of # appears at 1320 cm-1 together with an extrenely broad yC-O-C band.

EXAMPLE 6 5-[/2-trifluoromethyl-4,6-dinitrol-phenoxy]-2-nitro-benzaldehyde/Compound No. 6/ 8.4 g /0.024 mole/ of 3-[/2-trifluoromethyl-4,6-dinitro/-phenoxy3-benzaldehyde /prepared according to Example 3/are nitrated according to the method described in Example 5. Thus 6.0 g of the desired compound are obtained in the form of yellow crystals.

Yield 64%. Mp.: 112-122 C.

Brutto Formula : C14H608N3F3; molecular weight: 401 /calculated/ The characteristic fragments of the mass spectrum are as follows: m/e/r.i./ = 401 /140/ = F2C/No2/2C5H2OC6H3/NO/CHO 251 /220/ = F3C/NO2/2C6H2O 235 /1000/ = F3C/NO2/2C6H2 166 /500/ = OC6H3/NO2/CHO The 1H-NMR spectrum is an excellent example of easily recognizable and identifiable aromatic protons.

The large shift /10.25 ppm/ of the formyl proton can be attributed to the adjacent nitro group. The proton between the nitro groups /9.05 ppm/ gives a nice meta-coupling /J=3Hz/ with the proton between the trifluoromethyl and nitro group /8.82 ppm/.

In the IR spectrum the yCO band appears at 1700 cm-1.

111 Preparation of the fungicidal compositions EXAMPLE 7 Suspension concentrate ISCI Compound No. 4 50.0 % Ethylene glycol 8.0 % Nonyl-phenyl-polyglycol etcher/10 EO/ 5.0 % Polysaccharide 0.1 % Silicon oil 1.5% Water 35.4%.

EXAMPLE 8 Wettable powder IWPI Compound No.1 90.0% Highly dispersed silicic acid 5.0 % Dispersing agent 5.0 % EXAMPLE 9 Granules IGI Compound No. 6 5.0 % Ground limestone 69.0 % Ethylene glycol 3.0 % Highly dispersed silicic acid 5.0 % Sodium lignosulfonate 3.0 % Water 15.0% EXAMPLE 10 Dry flowable granules suitable for spraying IWGI Compound No.2 80.0 % Sodium lauryl sulfate 2.0 % Sodium lignosulfonate 7.0% Water 3.0 % China clay 8.0 % EXAMPLE 11 Emulsifiable concentrate IECI Compound No.3. 40.0% Xylene 12.0% Cyclohexanone 20.0 % Isophorone 20.0 % Polyoxy-ethylene-sorbitane monooleate 5.0 % Nonyl-phenyl-polyglycol-ether /EO=10/ 3.0 % EXAMPLE 12 Compound No.1. 20.0 % Xylene 60.0 % Isophorone 8.0 % Polyoxy-ethylene-sorbitol trioleate 5.0% Tributyl-phenyl-polyglycol ether /EO = 10/ 7.0% EXAMPLE 13 Seed-grain foil a/ Preparation ofthe 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 0.05-0.06 mm. /control foil/ b/Preparation ofa foil comprising the active ingredient One proceeds according to paragraph al except that to the solution used for the casting of the foil 0.120 g of compound No. 6 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 similar to that according to paragraph a/but comprises 1000 ppm of compound No. 6 as active ingredient.

One may also proceed by using as active ingredient in the place of Compound No. 6 a suspension of 0.0120 g of Compound No.3 in 5 ml of water. The foil thus obtained contains 100 ppm of the active ingredient.

111. Biological Examples In the following Examples the known 5-/2,6-dichloro-4-trifluoromethyl-phenoxy/-2-nitro-benzaldehyde /Compound A/ is used as reference compound.

EXAMPLE 14 Testing of fungicidal activity An agar plate 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 100-160 fold magnifying 25-30 spores shuld 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 Asperglllus niger lAl and Botrytis cinerea lBl Test Dose Colony growth in value numbers Colony growth Fungicidal compound in replicates as % of the activity in % No. ppm lAl lBl average 1 2 3 4 Average 1 2 3 4 Average lAl lBl lAl IBI 10000 2 2 3 3 2.5 3 3 2 2 2.5 30 30 70 70 2000 3 3 3 3 3 3 2 4 3 3 50 50 50 50 1 400 3 3 3 3 3 3 3 3 3 3 50 50 50 50 80 3 4 4 3 3.5 4 3 4 3 3.5 75 75 25 25 16 4 4 4 4 4 4 4 4 4 4 100 100 0 0 10000 2 3 3 2 2.5 3 3 3 2 2.75 30 40 70 60 2000 3 3 3 2 2.75 3 3 3 3 3 40 50 60 50 2 400 3 3 3 3 3 3 4 3 4 3.5 50 75 50 25 80 4 3 4 3 3.5 4 4 4 3 3.75 75 82-83 25 17-18 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 2000 1 2 1 2 1.5 1 1 2 1 1.25 5 2-3 95 97-98 3 400 2 3 1 2 2 2 3 2 2 2.25 10 20 90 80 80 3 2 3 2 2.5 2 3 3 3 2.75 30 40 70 60 16 4 4 3 3 3.5 4 3 4 3 3.5 75 75 25 25 10000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 2000 1 1 2 2 1.5 2 2 2 2 2 5 10 95 90 4 400 2 2 2 2 2 2 2 2 2 2 10 10 90 90 80 3 3 2 3 2.75 3 3 3 3 3 40 50 60 50 16 3 4 3 4 3.5 4 4 4 4 4 75 100 25 0 10000 2 2 2 2 2 2 2 2 1 1.75 10 7-8 90 92-93 2000 3 2 3 2 2.5 2 2 3 3 2.5 30 30 70 70 5 400 3 3 3 3 3 3 3 3 3 3 50 50 50 50 80 3 4 3 4 3.5 3 4 4 4 3.75 75 82-83 25 17-18 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 2000 1 1 1 1 1 1 1 1 1 1 0 0 100 100 6 400 2 2 2 2 2 2 2 2 1 1.75 10 7-8 90 92-93 80 3 2 2 3 2.5 2 2 2 2 2 30 10 70 90 16 3 3 4 4 3.5 3 3 4 4 3.5 75 62-63 25 37-38 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 IN 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 3 4 4 3.75 3 3 4 4 3.5 82-83 75 17-18 25 Id Control - 4 4 4 4 4 4 4 4 4 4 100 100 0 0 EXAMPLE 15 Testing ofherbicidal activity in glass-house The following test proves that the compounds of the present invention possess fungicidal and not herbicidal effect.

In growth plates /surface 1.64 cm2/ into a sandy soil Sinapsus arvensis and Setaria glauca seeds are sown /30 seeds into each plate; at a depth of 30 cm/ and the soil is watered to a total water capacity. Pre-emergent treatments are carried out immidiately after sowing and post-emergent treatments are accomplised 10 days afterthe shoting of the seedlings by using a spray prepared from 10 % emulsifiable concentrates of the test compounds. The spray is applied at such a rate that the dose should be 0.1; 0.33; 1; 3 and 9 kg of active ingredient/ha, respectively. The symptoms are expressed in % and the ED50 /median efficient dose/ is determined on the basis of these data for each test plant.

The results are summarized in Table 2.

TABLE 2 Test Dose Sinapis arvensis Setaria glauca compound kglha pre-emergent post- pre- post No. killing % ED50 emergent ED50 emergent ED50 emergent ED50 killing % killing % killing % 0.1 0 18 0 0 0.33 20 45 10 10 lAl 1 73 0.6 80 0.35 90 0.5 72 0.2 3 98 96 100 100 9 100 100 100 100 0.1 0 0 0 0 0.73 0 0 0 0 1 1 0 0 O X oo 0 > 9 0 3 0 0 10 0 9 0 0 20 0 0.1 0 0 0 0 0.33 0 0 0 0 2 1 0 so 0 > 9 0 > 9 30 9 3 0 10 10 40 9 0 30 20 50 0.1 0 0 0 0 0.33 0 0 0 0 3 1 0 ce 0 > 9 0 0 3 0 10 0 0 9 0 30 0 0 0.1 0 0 0 0 0.33 0 0 0 0 4 1 0 x 0 cc 0 cc 0 3 0 0 0 0 9 0 0 0 0 0.1 0 0 0 0 0.33 0 0 0 0 5 1 0 co 0 # 0 0 3 0 0 20 > 9 0 > 9 9 0 0 30 30 0.1 0 0 0 0 0.33 0 0 0 0 6 1 0 cc 0 > 9 0 cc 0 9 3 0 10 0 20 9 0 30 0 30

Claims (15)

1. Phenoxy benzaldehyde derivatives of the general Formula I

/wherein R1 and F3 stand for trifluoromethyl or nitro with the proviso that R1 and F3 are different; R2 is hydrogen or 3-formyl-phenoxy; X represents hydrogen or chlorine and Y stands for hydrogen or nitro/.

2. 3-[/5-chloro-4-trifluoromethyl-2-nitro/-phenoxy]-benzaldehyde.

3. 3-[/4-trifluoromethyl-2,6-dinitro/-phenoxy]-benzaldehyde.

4. 3-[/2-trifluoromethyl-4,6-dinitro/-phenoxy]-benzaldehyde.

5. 2,4-bis-/3-formyl-phenoxy/-1 -trifl uoromethyl-3,5-dinitro-benzene.

6. 5-[14-trifl uoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzaldehyde.

7. 5-[/2-trifluoromethyl-4,6-dinitro/-phenoxy]-2-nitro:benzaldehyde.

8. Process for the preparation of phenoxy-benzaldehyde derivatives of the general Formula I

wherein R1 and F3 stand for trifluoromethyl or nitro with the proviso that R1 and F3 are different; R2 is hydrogen or 3-formyl-phenoxy;; X represents hydrogen or chlorine and Y stands for hydrogen or nitro/ which comprises reacting 3-hydroxy-benzaldehyde or an alkali metal salt thereof in the presence of an inert diluent with a substituted benzene derivative of the general Formula II

/wherein R1, R2, R3, X and Y are as stated above and Hal represents halogen, preferably chlorine, isolating the phenoxy benzaldehyde derivative of the general Formula I/a

thus obtained from the reaction mixture íwherein R1, R2, R3, X and Y are as stated above/, if desired nitrating the compound of the general Formula l/a and isolating the compound of the general Formula l,b

thus obtained from the reaction mixture /wherein R1, R2, R3, X and Y are as stated above.

9. Use of the phenoxy benzaldehyde derivatives ofthe general Formula I according to Claim 1 as fungicidal agents.

10. Fungicidal composition or concentrate comprising as active ingredient in an effective amount at least one phenoxy benzaldehyde derivative of the general Formula I wherein R1, R2, R3, X and Y are as stated in Claim 1.

11. Process for combating fungal diseases of plants which comprises applying onto the plants, the fungal pests or the environment or the growing space thereof a phenoxy benzaldehyde derivative of the general Formula I according to Claim 1 or a compound as claimed in any one of claims 2 to 7.

12. a process as claimed in claim 8 substantially as hereinbefore described in any one of Examples 1 to 6.

13. A fungicidal composition or concentrate as claimed in claim 10, which further includes an inert carrier, diluent and/or auxiliary agent.

14. A composition or concentrate as claimed in claim 10, substantially as hereinbefore described in any one of Examples 7 to 13.

15. A process as claimed in claim 11 substantially as hereinbefore described in any one of Examples 14 or 15.