GB2167069A - Fungicidal 2-nitro-5-phenoxy-benzoic acid derivatives - Google Patents

Abstract

5-[(2-chloro-4-trifluoromethyl-5-nitro)phenoxy]-2-nitrobenzoic acid (and salts and the ethyl ester thereof), 5-[(2-trifluoromethyl-4-nitro)phenoxy]-2-nitrobenzoic acid ethyl ester or 5-[(3-chloro-4-trifluoromethyl- 2,6-dinitro-phenoxy]-2-nitrobenzoic acid ethyl ester may be used for preventing fungicidal attacks of cultivated plants. The fungicidal compounds according to the invention may be used in an amount of 0.0001 to 96% by weight in association with one or more solid and/or liquid carriers and optionally with other ingredients, preferably with surfactants and/or dispersing agents.

Description

SPECIFICATION Fungicidal composition and a method for preventing fungal infections of cultivated plants Technical field The invention relates to fungicidal compositions containing substituted 5-/phenoxy/-2-nitro-benzoic acid or its salt or ethyl ester derivative as active ingredient and their use for preventing fungal attacks of cultivated plants.

In the composition and method according to the invention 5-22-chloro-4-trifluoromethyl-5-nitro/ -phenoxy]-2-nitro benzoic acid or its salt or ethyl ester derivative, 5-[/2-trifiuornmethyl-4-nitrn/-phenoxyj-2- nitro-benzoic acid ethyl ester or 5-[/3-chloro-4-trifluoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzoic acid ethyl ester are used as active ingredient. The preferred salts are the sodium, potassium, ammonium, isopropyl-ammonium, allyl-ammonium-, ethanol-ammonium or diethyl-2-propinyl-ammonium salts.

Background art The US patent specifications Nos. 3,652,645, 3,776,715,3,983,168 and 4, 001,005 disclose different 5-/halogenphenoxy/-2-nitro-benzoic acid compounds containing no trifluoromethyl substituents and their salts, ester and amide derivatives and it is emphasized that these compounds are very effective pre- and post-emergence herbicides.

In the US patent specifications Nos. 3,798,276, 3,928,416 and 4,863,929 5-[4-trifluoromethyl-phenoxy]-2nitro-benzoic acids substituted with halogen, alkyl or trifluoromethyl in the 2nd and 6th-position of the phenoxy-moiety, their salts and ester derivatives are described, which also possess herbicidal activity.

As herbicidally active compounds are mentioned the 5-/substituted-phenoxy/-2-nitro-benzoic acids, their salts and ester derivatives substituted in the phenoxy moiety e.g. with halogen, nitro or trifluoromethyl. The general formula of the compounds described in he above mentioned US specifications covers the following compounds of the present invention,too: 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-2-nitro-benzoic acid and its salts, 5-[/2-trifluoromethyl-4-nitro/-phenoxy]-2-nitro-benzoic acid ethyl ester, 5-[/3-chloro-4-trifluoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzoic acid ethyl ester, and 5-[/2-ch loro-4-trifl uoromethyl -5-nitro/-phenoxy] -2-nitro-benzoic acid ethyl ester.

However, these compounds are not referred to in the specifications, the process for their preparation is not described, physical constants are not given, i.e. they have not been prepared yet. Nevertheless, for a man skilled in the art it is obvious that the four compounds mentioned above can possess only herbicidal activity.

Detailed description of the invention In the course of our experiments surprisingly we found, that these compounds possess not herbicidal but an excellent fungicidal activity, furthermore they are not phytotoxic and so they are very suitable for treating fungal infections of cultivated plants. They do not merely enlarge the variety of fungicides but also promote the conrol of fungi being resistant to known fungicides. They are optionally used in combination with other known fungicides.

Therefore the present invention provides a composition and method being suitable for treating fungal infections of cultivated plants which composition contains 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]- 2-nitro-benzoic acid or its salt or ethyl ester derivative, 5-[/2-trifluoromethyl-4-nitro/-phenoxy]-2-nitro- benzoic acid ethyl ester, or 5-[/3-chloro-4-trifluoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzoic acid ethyl ester as active ingredient in an amount of 0.0001 - 96 % by weight, admixed with one or more solid and/or liquid carriers, preferably ground natural minerals, inert solvents and optionally with surfactants, preferably anionic or nonionic emulsifying agents and/or dispersing agents and/or other additives.

The fungicidal compositions according to the invention can be formulated e.g. in form of wettable powders IWPI, emulsifiable concentrates /EC/, suspension concentrates /SIC/, various types of water-miscible solution concentrates ISCI water-soluble concentrates /WSC/, various granules IGI, IWGI, ULV compositions, foils, preferably seed-foils. In these compositions the active ingredients or the mixture thereof are admixed with solid or liquid carriers, solvents, optionally with other excipients.

The ingredients used in a composition according to the invention may for example be surface active agents, such as wetting agents, dispersing agents, emulsifying agents, anticakings, spreaders, antifoams, different agents which enhance the penetration and adhesion of the active ingredient, or enhance or maintain the biological activity thereof etc.

Suitable solid carriers and dilutents in a composition according to the invention include e.g. inert minerals, such as different kaolins, China clay earthes, attapulgite, montmorrilonite, micaschist, piroffilite, bentonite, diatomaceous earth or synthetic silicas of high dispersity, potassium carbonate, calcinated magnesia, dolomite, gypsum, tricalciumphosphate, Fuller's earthes, etc., further milled tobacco-stem or wood flour can also be used.

Suitable liquid carriers, diluents and solvents include e.g. water, organic and/or aqueous organic solvents, such as methanol, ethanol, n- and isopropanol, diacetone-alcohol, benzylalcohol; glycols, such as ethyleneglycol, diethylene-, triethylene- and propylene glycol, and the esters thereof, such as methylcellosolve, butyl diglycol; ketones, such as dimethylketone, methylethylketone, methylisobutylketone, n- or isopropylacetate, n- or isobutylacetate, amylacetate, isopropylmyristate, dioctylphtalate, dihexylphtalate, etc.; aromatic, aliphatic or alicyclic hydrocarbons, such as paraffin hydrocarbons, cyclohexane, cerosane, gasoline, benzene, toluene, xylene, tetraline, decaline; mixtures of alkylbenzenes; chlorinated hydrocarbons, such as trichloroethane, dichloromethane, perchloroethylene, dichloropropane, chlorobenzene, etc.; lactones, such as -butirolactone, etc.; lactames, such as N-methylpyrrolidone, N-cyclohexylpyrrolidone; acidamides, such as dimethyl formamide etc.; different vegetable- and animal oils, such as sunflower-seed oil, linseed oil, olive oil, soybean oil, castor oil, sperm oil etc.

The suitable wetting-, dispersing, emulsifying, adhesion-enhancing agents, anticakings and spreaders may be of nonionic or ionic type.

As ionic agents the following compounds can be mentioned: the salts of saturated or unsaturated carboxylic acids; sulphonates of aliphatic, aromatic or aliphatic-aromatic-hy drocarbons; sulphates of alkyl-, aryl- or aralkyl alcohols; sulphonates of the alkyl-, aryl- or aralkylesters and -ethers; sulphated vegetable or animal oils; alkyl-, aryl- or aralkylphosphate esters; the various salts of the above-mentioned compounds formed with alkali- or alkali-earth metals or with organic bases, such as different amines or alkanolamines.

For example; sodium-laurylsulphate, sodium-2-ethyl-hexylsulphate; sodium-, ethanolamine-, diethanolamine-, triethanolamine- or isopropylamine salt of dodecyl-benzenesulphonic acid; sodium salt of naphthalenesulphonic acid; sodium-diisooctylsulphosuccinate, sodium-xylenesulphonate; sodium- or calcium salt of petrole- sulphonic acid; soft soap; potassium-, sodium-, calcium-, aluminium- or magnesium-stearate, etc. The phosphate esters include e.g. phosphated alkylphenols- or esters of fatty-alcohols formed with polyglycols as well as their neutralized or partly neutralized forms with the above-mentioned cations or organic bases. Further, as anionic surface-active agent disodium-N-octadecylsulphosuccinate, sodium-N-oleyl 1-N-methyltrauzide, etc., as well as the different kinds of ligninesulphonates can be used.

Suitable nonionic wetting-, dispersing- and emulsifying agents include e.g. ethers of ethylene oxyde formed with alcohols having 10 to 20 carbona toms, such as stearylpolyxyethylene, oleylpolyoxyethylene; alkylphenol esters, such as the ester of stearinic acid or myristinic acid formed with polyethylene glycol or polyethylenglycololeate, etc.; ethylene oxide and propylene oxide block-polymers; partial esters offattyand oleic acids formed with hexitolanhydrides, such as the ester of sorbitol formed with oleic acid or stearinic acid or condensation products of the above compounds formed with ethylene oxide; tercier glycols, such as 3,6-dimethyl-4-octyn-2,6-diole or 4,7-dimethyl-5-decyn-4,7-diole; polyethyleneglycolthioethers, such as the ether of dodecylmercaptane formed with polyethylene-glycol etc.

Suitable spreading agents include e.g. alkali-earth-metal soaps, salts of sulphosuccinic acid ester, natural and synthetic water-soluble polymers, such as casein, starch,vegetable gums, arabic gum, cellulose ethers, methylcellulose ethers, methylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyvinylalcohol, etc.

Suitable antifoam agents include e.g. polyoxyethylene and polyoxypropylene blockpolymers of low molecular weight; octyl-, nonyl-, phenylpolyoxy-ethylene /wherein the number of the ethylene-oxide units are > 5/; higher alcohols, such as octylalcohol etc; special silicon oils etc.

Using the suitable additives the different compositions can be made compatible from colloid-chemical points of view with any kind of fertilizer-system. The pesticidal compositions thus prepared may comprise other known pesticidal agents and/or nutriments as active ingredient besides the compounds of the invention.

In the preparation of wettable powders /WP/ the active ingredient/s/as well as the other ingredient/s/, surfactant/s/ are admixed, round and homogenized. When a liquid surfactant is employed it may also be e.g.

sprayed onto the surface of the solid organic or inorganic carriers orto the powder mixture also comprising the solid active ingredient. Similar method is used in the case of liquid active ingredients. Alternatively the solid components ground previously may be suspended in organic solvents which contain the liquid surfactant, and this suspension may be e.g. spray-dried. So, the liquid surfactant is applied on to the surface of the solid active ingredient and diluent.

Emulsifiable concentrates lECI can be prepared e.g. by dissolving the active ingredient/s/together with one of the above mentioned surfactants and emulsifying agents in a water miscible solvent. The emulsifiable concentrate thus obtained can form a spray emulsion upon admixing with water /spontaneously or by mechanical action/ which is stable over a long period.

In the course of the preparation of a water-miscible solution concentrate ISLI, the active ingredient and the suitable water soluble additives are dissolved in water and/or a water-miscible solvent. This composition can be diluted with water to obtain a spray having the desired concentration.

In the course of the preparation of water-soluble liquid concentrate IWSCI the active ingredient and the suitable water-soluble additives are dissolved in water or a water-miscible solvent. The composition thus obtained may be diluted to obtain a spray having the desired concentration.

The solution concentrate containing the active ingredient may also be dispersed in water-miscible solvent using a suitable emulsifying agent, in this case invert emulsion can be obtained. If always the most suitable solvents and surfactants are choosen, the compositions thus obtained form stable dispersions upon admixing with water or water-miscible liquids where the particles /even they are of molecular size/ does not sedimentate even over a long period.

In the preparation of suspension-concentrates ISCI the wetting and dispersing agents are dissolved optionally by heating in the mixture of water /preferably ionexchanged water. Then an antifreeze component /preferably ethylene glycol or glycerol/ and the solid active ingredient/s//being in powder or crystalline form/ and optionally the anticaking component/e.g. Aerosil 200/ are admixed under continuous stirring to this solution. Thereafter this grain-liquid system /i.e. slurry/ is ground in a wet grinding-machine /e.g. in a closed Dyno-mill/ to the desired particle size, which is generally at most 5 Fm, in order to avoid sedimentation. After grinding, the mixture is homogenized optionally with antifoam and thickening agents /e.g. Kelzan S/. Optionally the order of the above steps may be changed or if desired, other components /e.g.

pigments etc./ may be added.

The solid active ingredients may be combined with other liquid, water-immiscible or water-miscible active ingredients. The solid active ingredients having a low melting point can be used up in the form of a melt with or without an emulsifying agent.

The preparation of the compositions is similarto that ofthe EC or SC compositions.

Granules /G/for direct use can be obtained by extruding or by coating a milled carrier/e.g. milled limestone/ or by adsorbing the liquid component/s/ by an milled carrier having absorptive properties.

Granules suitable for spraying /WIG/ can be obtained from a WP and/or SC formulations by an agglomeraton method e.g. granulation in a dragee pan using a thikening agent.

Diluting these compositions with water or inert diluent/s/ sprays, dusting powders comprising less than 5% by weight, preferably 1 to 0.01 % by weight of active ingredient can be obtained.

Such compositions can also be obtained by mixing the different sprays containing only one active ingredient just before use.

One of the preferred fungicidal composition according to the invention is the seed-foil. It is a well-known method in horticulture as well as in agriculture that in order to facilitate the sowing, to assure the uniform seed - and row-space, instead of hand-planting the seed-corns are incorporated into any kind of water-soluble foil and these foil-bands, that may contain the seed-corns in several rows are put into the soil.

The foil may be made of any kind of an inert, water-soluble material, e.g. polyvinylalcohol the only demand in connection with it is, that it should not be harmful to the seeds and the moisture content of the soil could decompose or optionally dissolve it. The active ingredient can be incorporated into the said seed-foil or the seeds previously treated with the active ingredients according to the invention are incorporated into the foil.

The most common method for controlling and preventing the attack of prasitic fungi are as follows: treating of the seeds, spraying or dusting. The fungicides, e.g. the treating agents, sprays or dusting powders have to be applied to the locus of the infection or to the locus where the infection is derived from.

In order to protect the seed-corns from infections and to control fungi infecting the seed-corns in the soil, the seed-corns are treated. Particularly the mildew-like conidiumic fungi jeopardize the seed-corns and seedlings. E.g. Fusarium graminearum and Fusarium moniliforme causing the toxic fusariosis of corn and Nigrospora oryzae causing the migrosporic dry-rot of maize are spread by seed-corns.

The treated seeds can be attached by numerous other sorts of fungi e.g. members of genera Rhizoctonia, Penicillium or Helminthosporium, each of them are mildew-like conidiumic fungi. The infections caused by these fungi can be controlled by different known fungicides, e.g. by captan [1,2,5,64etrahydro-N-/ trichloromethylthio/-phtalimide], applied in an amount of 0.5 to 0.6 kg calculated for 1 t of seeds.

The fungi damaging the foliage or/and crops/fruits/of the plants can be controlled by several kinds of treatment, e.g. by spraying or dusting. For instance, in case of apple the monilia is caused by Spilocea pomi /Fusicladium dendriticum/ or in case of grape-vine grey-mould is caused by Botrytis cinerae. These sorts of fungi are also conidiumic type and can controlled by using a spray comprising captan in an amount of 120g/100 litres of diluent.

The importance of conidiumic fungi is therefore emphasized as the compounds according to the invention are especially effective against them.

These fungi represent the Miniliales order of the Denteromycetes class and the predominant part of them are the vegetative multiplying forms of the ascomytes /Ascomytes class/. Their three different families cause especially great damages to cultivated plants.

By way of illustration some genere of these families are summarized in the following table.

a/ Moniliaceae family genera: species: Monilia /e.g. M. Fructigena/ Aspergillus /e.g. A. nigerl Penicillium /e.g. P. crustaceum/ Botrytis /e.g. B cinerea/ Verticillium /e.g. V. albo-atruml Cercosporella /e.g. C. herpotrichoidesl bl Dematiaceae family genera: species: Thielaviopsis /e.g. T. Basicolal Nigrospora /e.g. N. cryzae/ Spilocea /e.g. S. pomi synonim/ Cladosporium /e.g. C. fulvuml Helminthosporium /e.g. H. turcicum/ Cercospora /e.g. C. beticola/ Alternaria le.g.A. solanil Stemphylium /e.g. S. radicinum c/Tuberculariaceae family genera: species Fusarium /e.g. F. graminearum and different forms of F. oxysporum/ As it has already been mentioned, all above fungi have a sexed form, too, for example Spilocea pomi is known as Venturia inaequalis or Endostigma inaequalis.

The above mentioned genera of mildew-like conidiumic fungi include many thousands of dangerous varieties but the speciality of the above mentioned species is that a fungicide which is effective against one type of them can control all of the listed fungi.

The efficicacy of the compounds of the invention was tested on Aspergillus niger, Botrytis cinerea and 17 other conidiumic fungus species, but it is expected that the same data could have been obtained if any other fungus belonging to the order of Moniliales had been used. In the in vitro tests captan was used as conrol, the efficicacy is exporessed in ppm or mg/I. It is expected that the efficicacy of the compounds of the invention related to that of captan would be similar in field tests, too.

The novel compounds of the invention, their preparation, formulation and biological activity are illustrated by the following, non-limiting examples.

The compounds of the invention were identified e.g. on the basis of their 1H-NMR spectra. The numbering of the protons corresponds to that of formula ll/

Preparation of the active ingredient: Example 1 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxyl-2-nitro benzoic acid and its salts/compound No.1 and its salts Nos. 1/a- 1/fl a/ In a two-necked round bottom flask 33.6 g /0.6 molest of potassium hydroxyde were dissolved in 300 ml of dry methanol and 41.4 g of 3-hydroxy-benzoic acid were added to the solution. After sucking off the methanol 15 g of dry potassium carbonate, 78.0 g /0.3 moles/of 3,4-dichloro-6-nitro-benzotrifluoride and 300 ml of acetone were added and the mixture was refluxed for 8 hours.Then it was poured into 2 litres of water and acidified to pH 1 with concentrated hydrogen chloride. The precipitated beige solid was filtered and washed with water. Melting point: 182-186 C. Yield: 81.6 g /75.3 %/ in form of beige solid.

Cl4H7CIF3NO5 Molecular weight: 361 /calculated/ m/e /r.i./ = 361/ 510/= F3C/CI//NO2/C6H2OC6H4COOH 344/1901= F3ClClHNO2lC5H2OC6H4CO 316/ 130/=F3C/Cl/NO2/C6H2OC6H4 137/10001= OC6H4COOH IR spectrum: 1I CO = 1685, v as C-O-C= 1320, v s C-O-C= 1130, v as NO2 = 1535 cm-1.

b/ 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-2-nitro benzoic acid was prepared by nitrating 3-[/ 2-ch loro-4-trif luoromethyl-5-nitro/-phenoxy]-benzoic acid.

To a two-necked flask equipped with a magnetic stirrer and a feeding funnel 6.2 g /0.0171 moles/of 3-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-benzoic acid were charged and dissolved in the mixture of 12.5 ml of dichloromethane and 7.6 ml of acetic acid anhydride. Thereafter a nitration mixture /5.5 ml /0.08 moles/ of 65 % nitric acid and 5.4 ml of concentrated sulphuric acid/was added at 5 - 10 C under vigorous stirring and the mixture was stirred at room temperature for 3 hours. The dichloromethane was sucked off the residue was poured onto ice. The oil thus obtained was dissolved in dichloromethane and the organic phase was extracted with aqueous sodium hydroxide solution. The aqueous phase was acidified under cooling to pH 1 with concentrated hydrogen chloride. The product precipitated in the form of a solid.

Yield: 4.6 g /65%/ in form of yellow crystalls.

Melting point: 79 - 81 C.

C14H6O7N2C1 F3 Molecular weight: 406/calculated/ MS: the characteristic fragments are as follows: m/e /r.i.l = 406/ 530/ = F3C/Cl//NO2/C6H2OC6H3/NO2/COOH 389/ 70/ = F3C/Cl/lNO2lC6H2 224/1000/ = F3C/Cl/lNO2/C6H2 196/ 480/ = F3C/CI/C6H3OH 166/170/ C6H4/NO2/COOH.

1H-NMR: The sign of the H3 and H6 protons appears as a singulet at 83 = 8.128 and #6 = 7.975 ppm respectively.

The sign of H6 appears as dublet at #5 = 7.875 ppm due to the ortho-coupling /d, J5.6. = 8 Hz/. The signs of H2 and H6 are overlapped /8 = 7.05 ppm/.

IR: v CO = 1710 cm-1.

The salts of 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-2-nitro benzoic acid were prepared as follows: 6.1 g /0.015 moles/ of 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-2-nitro-benzoic acid prepared according to Example 1 were dissolved in 30 ml of diethyl ether and 0.9 g /0.015 moles/of isopropyl amine in 10 ml of diethyl ether were added to the solution and the precipitated salt was filtered off after cooling.

Yield: 5.0 g /70 %/.

M.p.: 203-208 C.

When preparing the sodium salt, solid sodium hydroxyde in equivalent amount was added. To yield ammonium salt ammonia gas was bubbled through the etheric solution until heat evolution ceased, while to obtain allyl-ammonium-, ethanol-ammonium- or diethyl-2-propinyl-ammonium-salts, the same procedure as described for the preparation of isopropyl-ammonium salt was followed. The product thus obtained are summarized in Table 1.

TABLE 1 Salt Name of the salts Yield Melting point No. C 1/a Sodiu m-5-[/2-ch loro-4-trifluoromethyl-5-nitrol- 82 248-252 -phenoxyj-2-nitro-benzoate 1/b Ammonium-5-[/2-chloro-4-trifluoromethyl-5-nitro/- 79 150-156 -phenoxy]-2-nitro-benzoate 1/c Isopropyl-ammonium-5-[/2-chloro-4-trifluoromethyl- 72 203-208 -5-nitro/-phenoxy]-2-nitro-benzoate 1 /d Allyl-ammonium-5-[/2-chloro-4-trifluoromethyl-5- 80 185-189 -nitro/-phenoxyj-2-n itro-benzoate 1/e Ethanol-ammonium-5-[/2-chloro-4-trifluoromethyl-5- 95 40-45 -nitro/-phenoxy]-2-nitro-benzoate Ihygroscopicl 1/f Diethyl-2-propyl-ammonium-5-[/2-chloro-4-trifluoro- 91 58-60 methyl-5-nito/-phenoxy]-2-nitro-benzoate In the 1H-NMR spectrums of the salts listed in Table 1 the aromatic protons appear at the same 3 values. H3 and H6/s/: 83 5 8.73 and #6 = 8.25 ppm respectively. H6 appears as dublet due to the ortho-coupling /#5 = 7.94 ppm /d, J5,6, = 9 Hz/. H2 and H6 are overlapped.

IR : v as CO2- = 1605 cm- /broad band/, vs CO2 = 1350 cm- /medium, sharp band/.

Example 2 5-[/2-trifluoromethyl-4-nitro/-phenoxyj-2-nitro-benzoic acid ethyl ester/compound No. 2/ a/ To a two-necked round bottom flask 10.0 g /0.06 molesl of 3-hydroxy-benzoic acid ethyl ester, 13.53 g /0.06 moles/of 2-chloro-5-nitro-benzotrifluoride and 8.3 g /0.06 moles/of potassium carbonate were charged and suspended in 100 ml of acetone. The mixture thus obtained was refluxed for 8 hours, then the potassium salt was filtered. The filtrate was evaporated and the residue was recrystallized.

Yield: 15 g /70.4%/in form of a beige solid.

M.p.:63 C.

C16H1205NF3 Molecular weight: 355/calculated/ MS : the characteristic fragments are as follows: m/e/r.i./ = 355 680/ = F3C/NO2/C6H3OC6H4COOC2H5 341/ 280/ = F3C/NO2/C6H3OC6H4COOCH3 327/ 300/ = F3C/NO2/C6H3OC6H4COOH 310/1000/ = F3ClNO2IC6H3OC6H4CO IR: the spectrum also proves the above structure: = 8.5/d, J35 = 2 Hz/, #5 = 8.22/dd, J53 = 2 Hz, J56 = 8 Hz/,#6 = 7.25, #4, = 7.92 /d, J4,5, = 8 Hzl, = = 7.7, #5, = 7.5 /dd, J5,4, = J5,4 = J6,6 = 8 Hzl, #6, = = 6.85 /d, J6,5 = 8 Hz/,#CH2 = 4.325 lq, J = 7 Hz/, 8CH3 = 1.325 ppm It, J = 7 Hz/.

b/ To a two-necked flask equipped with an internal thermometer and a magnetic stirrer 8.8 g /0.025 moles/ of 3-[/2-trifluoromethyl-4-nitro/-phenoxy]-benzoic acid ethyl ester were charged and dissolved in the mixture of 33.0 ml of dichloromethane and 19.8 ml of acetic acid anhydride. Then under external ice-cooling 4.2 ml /0.092 moles/of 65 % of nitric acid and 4.2 ml of 98 % sulphuric acid were added dropwise whereupon the internal temperature raised to 10 C. During the two-hour feeding a temperature of 10-15 C was maintained.

Then the solution was stirred at room temperature for further 3 hours. Dichloro methane was distilled off from the precipitated pale yellow solid and the residue was poured onto ice. The precipitated yellowish-white solid was recrystallized from 60 ml of methanol. Upon cooling the hot solution, crystalline solid precipitated out within a short time.

Yield: 6.8 g /85%/ in form of white solid.

M.p.: 100-101 'C.

C16H11O7N2O3 Molecular weight: 400/calculated/ MS: the fragments giving the mostintesive signs are as follows: m/e/r.i./ = 400/ 780/ = F3C/NO2/C6H3OC6H3OC6H3/NO2/COOC2H5 372/ 380/ = F3C/NO2/C6H3OC6H3/NO2/COOH 371/ 390/ = F3C/NO2/C6H3OC6H3/NO2/COO 355/1000/ = F3C/NO2/C6H3OC6H3/NO2/CO 280 / 370/ = F3/NO2/C6H3OC6H2CO 751 880/=C6H3 The 1H-NMR spectrum proves the above structure, too: #5 = 8.375/dd, J56 = 8 Hz/, J53 = 2Hz/, #5, = 7.975 ppm /d, J5,6, = the other aromatic protons give complex multiplets, #CH2 = 4.3/q, J = 7 Hz/, #CH3 = 1.3 ppm/t, J = 7 Hz/.

Example 3 5-[/3-chloro-4-trifluoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzoic acid ethyl ester/compound No.3/ a/In a two-necked round bottom flask in 5.0 g /0.03 moles/of 3-hydroxy-benzoic acid ethyl ester 4.15 g /0.03 moles/of dry potassium carbonate were suspended and 18.3 g /0.06 moles/of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 20 ml of acetone were added to this suspension under slow stirring, within 5 hours. The solution was stirred for further 20 hours at room temperature and the precipitated potassium chloride was filtered. Then the solution was evaporated and the residue was recrystallized from 60 ml of methanol. The yellowish-white solid bacame yellow on air.

Yield: 5.6 g /43 %/ in form of yellowish-white solid.

M.p.: 86-87 C.

C,6H,007N2CIF3 Molecular weight: 434.5/calculated/ MS: it is proved that the molecule contains only one chlorine and the isotopes having the mass number 35 and 37 give double peaks at the m/e value of 434/436 [389/391].

m/e Ir.i.l = 434/ 436 [740/280] = F3C/CI//NO2/2C6HOC6COOC2H5 389/ 391 [950/330] = F3C/CI//NO2/2HOC6H4CO 165/ 800/ = OC6H4COOC2H5 137/ 520/ = OC6H5COOH 121/1000/ = C6H5COO The 1H-NMR spectrum also proves the above structure: = = 8.46, #4, = 7.8 /dd, J4,5, = 7 Hz, J4,2, = 1.5 Hzl, 86, = 7.06/dd, J6,5 = 8 Hz, J6,2 = 2 Hzl, 3CH2 = 4.275 /q, J = 7 Hz/, #CH3 = 1.3 ppm /t, J = 7 Hz/.

The NO2 band proves, that more than one NO2 groups are present The asymmetric and symmetric valency-vibration-bands of the C-O-C bond are very intensive at 1150 and 1300 cm-1.

b/ The nitration is carried out duly followed the procedure of Example 2. When recovering the product, the residue solidified immidiately after pouring onto ice, and after recrystallization from 60 ml of methanol white product is obtained.

Yield: 6.8 g /83.5 %/ in form of a white solid.

M.p.: 95-97 C C16H9O9N3ClF3 Molecular weight: 479.5 /calculated/.

The MS proves the presence of one chlorine, the intensity ratios correspond to the frequency of the appearence of the isotops. The most important fragments are the followings: m/e /r.i./ = 497/481 [ 500/160] = F3C/Cl//NO2/2C6HOC6H3/NO2/COOC2H5 451/453 [ 310/120] = F3C/Cl//NO2/2C6HOC5H3/NO2/COOH 434/436 [1000/340] = F3C/CI//NO2/2C6HOC6H3/NO2/CO 165/660/ = OC6H4COOC2H2 The 1H-NMR spectrum also proves the above structure: #5 = = 8.55,5, = 7.9 /d, J5,6 = 8 Hz I, 82, = 7.1 /d, J2,6, = 1.5 Hz/, #5, = 7.025 /dd, J6,5, = 8 Hz, J6,2 = 1.5 Hzl, 8CH2 = 4.275 /q, J = 7 Hz/, 8CH3= 1.25ppm/t,J = 7 Hz/.

IR: In case of the nitro-derivative thev C-O-C bands appear at higher value of wave number /1150 and 1350 cm-1/.

Example 4 5-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]-2-nitro benzoic acid ethyl ester/compound No.4/ a/The procedure of Example 3 was followed. The product was dissolved in 50 ml of methanol, cooled and after layering some methanol onto it, yellowish-white solid precipitated upon stirring. The solid was filtered and washed with some cold methanol.

Yield: 6.0 g /51.3 %/ in form of yellowish-white solid.

M.p.: 64-65 C.

C16H11O5NCLF3 Molecular weight: 389.5/calculated/ The MS proves that the compound contains only one chlorine as the two greatest fragments give a double sign corresponding to the ratio of 35CI and 37CI isotopes.

m/e Ir.i.l = 389/ 391 [750/260] = F3CI//NO2/C6H2OC6H4COOC2H5 344/ 346 [870/280] = F3C/Cl//NO2/C6H2OC6H4CO 165/ 550/ = OC6H4COOC2H5 121/1000/ = C6H5COO The 'H-NMR spectrum also proves the above structure: 86=8.07 /d, J63 = 1 Hz/,83 = 8.9/d,J36 = 1 Hz/, 84, = 8 Hz/, 86, = 6.95 /J6,5, = 7Hz/,8CH2 = 4.25 /q,J =7Hz/,8CH3= 1.3ppm/t,J =7Hz/.

b/ The procedure of Example 2 was followed except that 3-[/2-chloro-4-trifluoromethyl-5-nitro/-phenoxy]- benzoic acid ethyl ester was nitrated instead of 3-[/2-trifluoromethyl-4-nitro/-phenoxy]-benzoic acid ethyl ester. The yellow solid precipitating upon pouring the solution onto ice, solidifies after standing and becomes breakable. It is recrystallized from 50 ml of methanol.

Yield: 7.15 g /82.2 /O/ in form of yellowish-white solid.

M.p.: 83-84 C C16H1007N2C1 F3 Molecular weight: 434.5 /calculated/.

MS: all the fragments contain chlorine. Characteristic fragments are as follows: m/e /r.i.l = 434/4361 580/200/ = F3C/Cl//NO2/C6H2OC6H3/NO2/COOC2H5 406/408/ 150/50/ = F3C/Cl//NO2/2C6H2OC6H3/NO2COOH 389/391/ 450/150/ = F3C/Cl/NO2/C6H2OC6H3/NO2CO 224/226/1000/350/ = F3C/CI//NO2/C6H2 194/380/ = F3C/CL/C6H2O 166/260/ /C6H3/NO2/COOH IR: the strenghtening of v NO2 band as well as the desplacement of v CO band can be observed/from 1705 cm-1 to 1725 cm Formulation examples Example 5 Suspension concentrate ISCI Active ingredient/compound No.2/ 50 % by weight Ethylene glycol 8.0 % by weight Nonylphenyl-polyglycol ether/10 EO/ 5.0 % by weight Polysaccharide 0,1 % by weight Silicone oil 1.5 %byweight Water 35.4 % by weight Example 6 Wettable powderl WPI Active ingredient/compound No.1/ 90.0 % by weight Silica of high dispersity 5.0 % by weight Dispersing agent 5.0 %byweight Example 7 Granule IGI Active ingredient/compound No.3/ 5.0 % by weight Limestone ground 69.0 % by weight Ethylene glycol 3.0 % byweight Silica of high dispersity 5.0 % by weight Sodium ligninsulphonate 3.0 % by weight Water 13.5 % by weight Example 8 Dry flowable granule /WG/ Active ingredient/compound No. 2/ 80.0 % by weight Sodium laurylsulphate 2.0 % by weight Sodium ligninsulphonate 7.0 % by weight Water 3.0 % by weight Kaolin 8.0 % by weight Example 9 Water-soluble liquid concentrate /WSC/ Active ingredinet/compound No. 1/d/ 30.0 % by weight Ethylene glycol 5.0 % by weight Nonyiphenyl polyglycol ether 2.0 % by weight /EO= 10, e.g.Arcopal N-100/ Water /ionexchanged/ 63.0 % by weight Example 10 Emulsifiable concentrate IECI Active ingredient/compound No.2/ 40.0 % by weight Xylene 12.0 % by weight Cyclohexanone 20.0 % by weight Isoforone 20.0 % by weight Polyoxyethylene-sorbitane monooleate 5.0 % by weight Nonylphenyl-polyglycbl ether 3.0 % by weight Example 77 Seed-foll a/T0 615 g of water having a temperature of 60 C 80 g of polyvinylalcohol /of the type RHODOVIOL 4/125n P, the viscosity of an aqueous solution thereof is 4 cP at 20 C, hydrolisation degree 89 mole %/were charged under stirring.After dissolution 20 g of polyvinylalcohol /of the type RHODOVIOL 30/20 m, the viscosity of a 4 % aqueous solution thereof is 30 cP at 20 "C, hydrolisation degree 98 mole %/ and 20 g of glycerol were added and vigorously stirred until a homogenous solution was obtained. Thereafter the solution was allowed to stand while the bubbles could escape. The solution thus obtained was poured onto a glass sheet in a thickness of 0.5 mm using a doctor knife and dried at room temperature. The foil thus obtained comes off from the glass sheet, its thickness is 0.05 - 0.06 mm, it is easy to handle and has absorptive properties control foil.

b/ The procedure described above was followed but a solution containing 0.12 g of active ingredient compound No.6/ suspended in 5 ml of water was used forthe foil casting. After bubble release and casting, a foil having similar properties as the control foil but containing 1000 ppm of active ingredient was obtained.

c/ Following the procedure of item b/ but using a solution containing 0.012 g active ingredient/compound No.3/ suspended in 5 ml of water for the casting, a foil containing 100 ppm active ingredient was obtained.

dl Following the above procedure a foil comprising any compound according to the invention can be obtained.

Example 12 Fungicidal activity In order to determine the fungicidal activity of the compounds according to the invention the "poisioned" agar-sheet-method was used. To the compositions containing the compounds to be tested, water and potato-agar culture medium containing 2 % of dextrose were added in an amount which was sufficient to reach the desired concentration of the active ingredient to be tested.

The culture medium containing the compound to be tested in the desired concentration was poured into Petri dishes, allowed to solidify and inoculated with mycellium-disc of the same size cut out from pure fungus cultures. Thereafter the Petri-dishes were incubated for 3-7 days under conditions meeting the demands of the fungi to be tested.

The evaluation was carried out by measuring the diameter of the mycelliums and the ratio of the diameter of the treated and untreated cultures was calculated. If the diameter of the treated culture was the same as that of the untreated control, the protection was considered to be 0%.

The test result obtained by different active ingredient concentrations are summarized in Tables 2 and 3. As test fungi, Fusarium graminearium, Stemphylium radicium and Aspergillus niger, while as control compound captan were employed.

The data of the tables show that the compounds according to the invention possess similarly good or better activity than the known captan.

TABLE 2 Activity in % of protection Active Number of the active ingredient Cap tan ingredient 1 2 3 4 control conc. in ppm Fusarium graminearum 500 100 80 100 100 90 100 100 64 90 78 71 20 90 64 76 72 30 4 80 61 74 70 8 Stemphylium radicinum 500 100 69 99 100 84 100 100 69 84 88 72 20 73 66 75 70 54 4 71 47 66 61 35 Aspergillus niger 500 '94 82 100 89 86 100 94 79 86 75 70 20 82 78 78 76 30 4 80 66 76 64 7 TABLE 3 Activity in % of protection Active ingredient Number of the active ingredient Cap tan conc. in ppm 1 11a 11b 11c lId control Fusarium graminearum 500 100 100 100 100 100 90 100 100 90 88 88 100 71 20 90 63 65 70 83 30 4 80 51 47 55 77 8 Stemphylium ra dicinum 500 100 91 91 88 100 84 100 100 79 79 67 100 72 20 73 54 41 58 73 54 4 71 52 24 40 61 35 Aspergillus niger 500 94 90 93 90 100 86 100 94 83 58 82 94 70 20 82 72 33 35 86 30 4 80 53 25 17 81 7

Claims (8)

1. Fungicidal composition for treating of fungal infections of cultivated plants, which comprises in an amount of 0.0001 to 96 % by weight a compound selected from 5-[/2-chloro-4-trifl uoromethyl-5-nitro/ -phenoxy]-2-nitro-benzoic acid or its salts or ethyl ester derivative,5-[/2-trifluoromethyl-4-nitro/-phenoxy]-2- nitro-benzoic acid ethyl ester, 5-[/3-chloro-44rifluoromethyl-2,6-dinitro/-phenoxy]-2-nitro-benzoic acid ethyl ester as active ingredient in association with one or more solid and/or liquid carriers and optionally with other ingredient, preferably with surfactants and/or dispersing agents.

2. The composition as claimed in Claim 1,which comprises the sodium-, ammonium-, isopropylammonium or allyl-ammonium salt of 5-[12-chloro-4-trifluoromethyl-5-nitrol-phenoxy]-2-nitro-benzoic acid as active ingredients.

3. Method for treating fungal infections of cultivated plants, which comprises treating the soil, the seeds of the plants, the plants or a part of the plants with fungicidally effective amount of a compound selected from 5-[12-chloro-4-trifluoromethyl-5-nitrol-phenoxy]-2-nitro benzoic acid or a salt or ethyl ester derivative thereof,5-[/2-trifluoromethyl-4-nitro/-phenoxy]-2-nitro-benzoic acid ethyl ester or 5-[/3-chloro-4 trifluoromethyl-2,6-din itro/-phenoxy]-2-nitro-benzoic acid ethyl ester as active ingredient.

4. Method as claimed in Claim 3, which comprises using 5-[/2-chloro-4-trifluoromethyl-nitrol-phenoxy]-2- nitro-benzoic acid as active ingredient.

5. 5-[(2-chloro-4-trifluoromethyl-5-nitro)phenoxy]-2-nitro benzoic acid and salts and the ethyl ester thereof, 5-[(2-trifluoromethyl-4-nitro)-phenoxy]2-nitro benzoic acid ethyl ester, 5-[(3-chloro-4 trifluoromethyl-2,6-dinitro-phenoxyj-2-nitro benzoic acid ethyl ester.

6. A fungicidal composition including one or more of the compounds of claim 5, together with one or more solid and/or liquid carrier and optionally further adjuvants.

7. A composition as claimed in claim 6, substantially as hereinbefore described in any one of Examples 5 to 11.

8. A composition as claimed in claim 6 or claim 7, wherein the salt of 5-[(2-chloro-4-trifluoromethyl-5nitro)-phenoxy]-2-nitro benzoic acid is one of the salts set out in Table 1.