DE3539927A1 - FUNGICIDAL AGENT - Google Patents

Abstract

1 The invention relates to a composition for combating fungi pests of useful plants, characterized in that it is used as active ingredient in an amount of 0.0001-96% by weight of 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 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 and one or more solid and / or liquid carriers and optionally surface-active agents and / or dispersants.

Description

The invention relates to fungicidal agents for combating fungi pests of useful plants, which contain a substituted 5-phenoxy-2-nitro-benzoic acid or a salt or the ethyl ester thereof as the active ingredient.

The compositions according to the invention contain as active ingredient 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 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 .

Of the salts, the sodium, potassium, ammonium, isopropylammonium, allylammonium, ethanolammonium and diethyl-2-propynylammonium salts are advantageous.

US Pat. Nos. 3,652,645, 3,776,715, 3,983,168 and 4,001,005 described 5-halophenoxy-2-nitro-benzoic acids and their salts, esters and amides which do not contain trifluoromethyl groups; these compounds were clearly identified as very effective pre- and post-emergent / pre- and post-emergence / herbicides.

In US Pat. Nos. 3,798,276, 3,928,416 and 4,063,929, 5- / 4-trifluoromethylphenoxy / -2-nitro-benzoic acids, their salts and esters were placed under protection, which on the phenoxy part of the

Molecule in positions 2 and 6 carry hydrogen, halogen, alkyl or trihalomethyl substituents and also have herbicidal effects.

In US Pat. Nos. 4,164,409, 4,164,408 and 4,164,410, 5- / substituted phenoxy / -2-nitro-benzoic acids and salts and esters thereof were described which, inter alia, are represented on the phenoxy part of the molecule by hydrogen, Halogen, nitro or trifluoromethyl are substituted. The compounds according to the invention fall under the general formulas of the above three patents:

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;

5 - [/ 2-Chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid ethyl ester.

The above compounds are not mentioned in the cited patents, the production method thereof is not disclosed, and their physical constants are not given, i.e. the compounds in question were not produced. On the basis of the disclosure of the patent specifications, the person skilled in the art could only conclude that the four compounds mentioned could exclusively exert a herbicidal effect.

It has surprisingly been found that the above substituted 5-phenoxy-2-nitrobenzoic acid derivatives do not exert herbicidal but, in an unexpected manner, an excellent fungicidal effect and are also not phytotoxic. The compounds according to the invention not only represent an expansion of the selection of known fungicidal agents, but also enable effective control of pathogenic fungi strains that are already resistant to known fungicidal agents, optionally in the form of combinations formed with known fungicidal active ingredients.

The invention relates to a composition for combating fungi pests of useful plants, which contains 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] as an active ingredient in an amount of 0.0001-96% by weight. -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 5 - [/ 2-Trifluoromethyl-4-nitro / -phenoxy] -2-nitrobenzoic acid ethyl ester or 5 - [/ 3-chloro-4-trifluoromethyl-2,6-dinitro / -phenoxy] -2-nitro-benzoic acid ethyl ester and one or contains several solid and / or liquid carriers, preferably ground, natural minerals or inert solvents and optionally surface-active agents, preferably anionic or nonionic emulsifying agents and / or dispersing agents.

The invention also relates to a method for controlling fungi pests of useful plants, in which the soil, the seeds of the useful plant, the plants or a part thereof are advantageously used as active ingredient in an amount of 0.0001-20% by weight 0.01-5% by weight with 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 5 - [/ 2-trifluoromethyl-4-nitro / -phenoxy] -2-nitrobenzoic acid ethyl ester or 5 - [/ 3-chloro-4-trifluoromethyl-2,6-dinitro / - phenoxy] -2-nitro-benzoic acid ethyl ester treated.

The active compounds according to the invention can be formulated into fungicidal compositions in a manner known per se. These compositions can, for example, in the form of wettable powders / WP /, emulsifiable concentrates / EC /, suspension concentrates / SC /, water-miscible solution concentrates / SL /, water-soluble concentrates / WSC /, granules / G /, / WG /, in ULV- Compositions / ultra-low-volume / or foils / such as seed foils / etc. are available. These compositions are produced by mixing the active ingredient / or the active ingredients / with suitable solid carriers and / or with liquid diluents and, if appropriate, with other auxiliaries.

Surfactants, e.g. Wetting agents, suspending agents, dispersing agents, emulsifying agents, agents preventing knot formation, adhesives, "anticaking" agents, agents that promote penetration or that maintain or increase the biological effectiveness, antifoam agents, etc. are used.

Suitable solid carriers are inactive mineral substances such as various types of kaolin, china clay, attapulgite, montmorillonite, mica schist, pyrophillite, bentonite, diatomaceous earth / or highly dispersed synthetic silicas, calcium carbonate, calcined magnesium oxide, dolomite, gypsum, tricalcium phosphate, fuller's earth, etc./ or Substances of vegetable origin / e.g. ground tobacco leaf stem, wood flour, etc./ can be used.

Various solvents, such as water and organic solvents, can be used as suitable liquid diluents

Solvents, mixtures of water and various solvents such as methanol, ethanol, n- and isopropanol, diacetone alcohol, benzyl alcohol; Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, esters of the above compounds such as Cellosolv, butyl diglycol; Ketones e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone etc; Esters, e.g., ethyl acetate, n- and isopropyl acetate, n- and isobutyl acetate, amyl acetate, miristyl acetate, dioctyl phthalate, dihexyl phthalate, etc .;

aromatic, aliphatic and alicyclic hydrocarbons such as paraffins, cyclohexane, kerosan, gasoline, benzene, toluene, xylenes, chlorinated hydrocarbons e.g. trichloroethane, dichloromethane, perchlorethylene, dichloropropane, chlorobenzene, etc .; Lactones such as N-methyl-pyrrolidone, N-cyclohexyl-pyrrolidone; Acid amides such as dimethylformamide, etc., vegetable and animal oils such as sunflower oil, linseed oil, rapeseed oil, olive oil, soybean oil, castor oil, sperm oil, etc., can be used.

The suitable wetting, dispersing, emulsifying, coupling and anti-aggregating agents can be ionic or non-ionic.

As the ionic surface active agent, there can be used, for example, salts of saturated or unsaturated carboxylic acids; Sulfonates of aromatic, aliphatic and aliphatic-aromatic hydrocarbons; Sulfates of alkyl, aryl, and aralkyl alcohols; Sulfonates of alkyl, aryl, and aralkyl esters and ethers; Sulfonates of condensation products of phenol, cresol and naphthalene; sulfated vegetable and animal oils; Alkyl, aryl and aralkyl phosphate esters or those with alkali metals, alkaline earth metals or salts of the above compounds formed with organic bases / such as various amines, alkanolamines, etc. /. Advantageous representatives of the ionic surfactants are the following compounds:

Sodium lauryl sulfate, sodium 2-ethylhexyl sulfate; the sodium, ethanolamine, diethanolamine, triethanolamine or isopropylamine salt of dodecylbenzenesulfonic acid; Sodium mono- and diisopropyl naphthalene sulfonate; Sodium naphthalene sulfonate; Sodium diisooctyl sulfosuccinate; Sodium xylene sulfonate; the sodium or potassium salt of petroleum sulfonic acid; Soft soaps; Potassium, sodium, calcium, aluminum and magnesium stearates, etc. As phosphate esters, esters of phosphated alkylphenols or fatty alcohols formed with polyglycol or the forms thereof partially or completely neutralized with the above-mentioned cations or organic bases can be mentioned. As further examples of the ionic surfactants, disodium N-octadecyl sulfosuccinate, sodium N-oleyl-N-methyl tauride, etc., and the various lignosulfonates can also serve.

Suitable nonionic wetting, dispersing and emulsifying agents are, for example, the ethers of ethylene oxide formed with C [deep] 10-20 alcohols [e.g. Stearyl-poly / oxyethylene /, oleyl-poly / oxyethylene / etc.]; esters formed with alkylphenols / e.g. the esters of stearic acid and miristic acid formed with polyethylene glycol or polyethylene glycol oleate etc./; Block polymers of ethylene oxide and propylene oxide; partial esters of fatty and oleic acids with hexitol anhydrides / e.g. Esters of sorbitol with oleic acid or

Stearic acid / or the condensation products of the above compounds formed with ethylene oxide; tertiary glycols / e.g. 3,6-dimethyl-4-octyne-2,6-diol or 4,7-dimethyl-5-decyne-4,7-diol /, polyethylene glycol thioether / e.g. dodecyl mercaptan ethers formed with polyethylene glycol, etc./.

Alkaline earth metal soaps, sulfosuccinic acid ester salts, natural and synthetic water-soluble macromolecules / e.g. Casein, starch, vegetable gum, gum arabic, cellulose ether, methyl cellulose ether, methyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, etc. are used.

Suitable antifoam agents include, for example, poly / oxyethylene /, poly / oxypropylene / small molecular weight block polymers; Octyl-, nonylphenyl-poly / oxyethylene / number of ethylene oxide units> 5 /, long-chain alcohols / e.g. Octyl alcohol etc./, special silicone oils etc. can be used.

With the use of suitable additives, compositions that are compatible with the various synthetic fertilizer systems from a colloid-chemical point of view can be produced. The fungicidal compositions according to the invention can furthermore contain known pesticidal agents and / or nutrients.

The wettable spray powders / WP / can be produced, for example, in such a way that the active ingredient (s), the auxiliary (s) and the surfactant (s) are mixed with the carriers, the mixture is ground and finally homogenized. When using liquid surface-active substances, one can proceed in an alternative way: that the liquid surface-active substance on the solid organic substance or on the inorganic carrier /z.B. by spraying / applying. Liquid active ingredients can be formulated in a similar way. Liquid surface-active substances can furthermore be used in such a way that the previously ground solid components are suspended in an organic solvent which contains the liquid surface-active agents. The suspension thus obtained can be dried, for example, by spraying. In this way the surfactant is applied to the surface of the solid support or diluent.

The emulsifiable concentrates can be prepared in such a way that the active ingredient / or the active ingredients / and the abovementioned emulsifying agents are dissolved in a water-immiscible solvent. The emulsifiable concentrate obtained in this way forms, spontaneously or after a slight mechanical action, a spray emulsion which can be stored for a long time.

The water-miscible solution concentrates / SL / can be prepared in such a way that the active ingredient and the suitable water-soluble auxiliaries are dissolved in water or in a water-miscible organic solvent and a spray liquor of the appropriate concentration is prepared from this solution by dilution with water.

The water-soluble liquid concentrates / WSC / can be prepared in such a way that the active ingredient or active ingredients are dissolved in water or in an organic solvent that can be mixed with water. This solution can be diluted with water to produce a

Spray liquor of the desired concentration can be prepared.

The aqueous solvent concentrate of the active ingredient can be dispersed in a water-immiscible liquid by selecting a suitable emulsifier; the s. g. obtained invert emulsions. By suitable selection of the solvent and the surface-active agent, compositions can be produced which, after mixing with water or a water-immiscible solvent, produce certain - even molecularly - dispersed systems which are stable for a longer period of time and remain unchanged.

The suspension concentrates / SC / are prepared in such a way that in the mixture of water / advantageously ion-exchanged water / and an anti-freeze agent / advantageously ethylene glycol or glycerine / the wetting or dispersing agents, if necessary, are dissolved with heating. The solid / powdery or crystalline / active ingredients and optionally the "Anticaking" /z.B. Aerosil 200 / added. The obtained particle-liquid system / broth / is with the help of wet grinding devices /z.B. in a closed Dyno mill / brought to the desired particle size / taking into account the storage stability, this is a particle diameter of at most 5 micrometers /. If necessary, an antifoam or thickener / e.g. Kelzan S / mixed in during the homogenization. The order of

The addition of the components can be changed or, if necessary, additional components can be added / e.g. Dyes /. In addition to the solid active ingredient, liquid active ingredients that are immiscible or immiscible with water can be used as combination partners. The solid active ingredients having a low melting point can also be added in the melt without an emulsifier or mixed with the emulsifier.

The ULV preparations can be made similar to the EC agents / or occasionally the SC agents /.

The granules / G / suitable for immediate use can be produced by extrusion, layering using a granular carrier / e.g. Limestone grist / or by the absorption of the liquid component by a carrier with a large sorbent capacity. The granules / WG / suitable for spraying can be extracted from the WP and / or SC concentrates with the help of an agglomeration technology / e.g. in a coating pan / with the use of binders.

The spray liquors or dust compositions which can be used in agriculture can be prepared in a known manner from the above compositions by dilution with water or inert solid carriers. The active ingredient content of these crop protection agents is generally below 5% by weight and is advantageously 0.01-1% by weight.

One can also proceed in such a way that the various spray liquors, each containing an active ingredient, are mixed with one another before use.

The seed foils represent an advantageous embodiment of the solid fungicidal agents according to the invention. It is known in horticulture and other agricultural processes that, in order to facilitate the sowing of the seeds and ensure uniform seed and row spacing, the seed grain is put into water-soluble foils instead of being sown by hand are incorporated and these film strips / tapes / - which may contain the seeds in several rows - are inserted into the ground. The film can be made of any water-soluble material that is inert towards the seeds / z.B. Polyvinyl alcohol / consist. In relation to the film material, the requirements are made that these do not damage the seeds and that they are decomposed or, if necessary, dissolved in the soil under the action of moisture. The seed foil can contain the active ingredients according to the invention incorporated into the foil, or the seeds treated with the active ingredients according to the invention can be embedded in the foils.

To control plant pests and prevent infection caused by fungi, the following crop protection measures are most common: dressing, spraying and dusting. The fungicidal agents according to the invention - e.g. dressing agents, sprays, dusting agents - can be applied to those parts of the plant or in the vicinity thereof where the infection takes place or where the pest can spread.

The dressing is used to produce infection-free seeds and to combat the soil infecting fungi. The seed and the germinating plants are primarily endangered by the mold-like conidia fungi. Reference is made, for example, to the following pests: Fusarium graminearum and Fusarium moniliforme, which cause toxic fusariosis on maize; Nigrospora oryzae, which causes nigrosporic dry rot and which can also damage the seeds.

The pickled seeds can also be attacked by numerous other fungi, e.g. members of the Rhizoctonia, Penicillium and Helminthiosporum genus. The above pests belong to the family of the so-called mold-like conidia fungi. These pests can be combated by various known fungicidal agents, for example with the well-known captan [1,2,5,6-tetrahydro-N- / trichloromethyl / -phthalmide], which is available in a dose of 0.5-0.6 kg / 1000 kg of seeds can be used.

The fungi that endanger the leaves and the crop / fruit / plant can be prevented by treating the plant population / e.g. Spraying and dusting / fought. The monilia on apple can be caused, for example, by Monilia fructigena and the venturial scabies by Spilocea pomi / Fusicladium dendriticum /. The gray rot of grapevines is caused by Botrytis cinerea. To eradicate these types of fungi - which belong to the group of mold-like conidic fungi - the above-mentioned captan is used in a can of 120 g / 1000 l of spray liquid.

The fungicidal agents according to the invention are particularly useful for combating mold-like conidic ones

Suitable for mushrooms.

These fungi form the Miniliales genus of the Deuteromycetes class; the vast majority of these fungi belong to the vegetative forms of tubular spores / Ascomycetes class /. Three families of these fungi in particular cause severe damage to crop production.

The main gender and species of the above family are listed in the tables below, for example only.

a / Moniliaceae family:

Gender: 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 /

Cercosporella / e.g. C. herpotrichoides /

__________________________________________________________________________

b / Dematiaceae family:

Gender: Species

__________________________________________________________________________

Thielaviopsis / e.g. T. Basicola /

Nigrospora / e.g. N. oryzae /

Spilocea / e.g. S. pomi synonym

Fusicladium dendriticum /

Cladosporium / e.g. C. fulvum /

/ Continuation of table b /

Gender: Species

___________________________________________________________________________

Helminthosporium / e.g. H. turcicum /

Cercospora / e.g. C. beticola /

Alternaria / e.g. A. solani /

Stemphylium / e.g. S. radicinum /

___________________________________________________________________________

c / Tuberculariaceae family:

Gender: Species

___________________________________________________________________________

Fusarium / e.g. F. graminearum

and different shapes

by F. oxysporum /

___________________________________________________________________________

As already mentioned above, the sexual tubular forms of the above fungi are also present, e.g. the Spilocea pomi are known under the names Venturia inaequalis or Endostigme inaquealus.

Several thousand dangerous pathogenic species of the mold-like conidic fungi are also known; only a few families were named above as examples. These strains are characterized by the fact that they have fungicidal active ingredients against effective contact are sensitive, although there are certain - but not significant - differences in sensitivity. The activity data given for Aspergillus niger and Botrytis cinerea species and for 17 conidia species are generally characteristic of the entire Moniliales genus. The above tests were carried out in vitro, compared with the captan standard and given in ppm or mg / ml. However, these values are also valid for outdoor conditions.

Further details of the present invention can be found in the examples below without restricting the scope of protection to these examples.

In the preparation examples, for the [high] 1H-NMR spectroscopic data, that of the general formula I / I /

described identification method is used. The designation of the position of the individual protons differs from the designation used according to the nomenclature, but the method used enables uniform spectroscopic utilization.

A. Manufacture of the active ingredients

example 1

5 - [/ 2-chloro-4-trifluoromethyl-2-nitro / -phenoxy] -2-nitro-benzoic acid

[Compound No. 1. and its salts 1a / -1f /]

a / 300 ml of anhydrous methanol and 33.6 g / 0.6 mol / potassium hydroxide are weighed into a two-necked round bottom flask and, after dissolution, 41.4 g of 3-hydroxy-benzoic acid are added. After removal of the methanol, 15 g of anhydrous potassium carbonate, 78.0 g / 0.3 mol / 3,4-dichloro-6-nitro-benzotrifluoride and 300 ml of acetone are added to the residue. The reaction mixture is refluxed for 8 hours, cooled, poured into 2 liters of water and acidified to pH 1 with concentrated hydrochloric acid. The beige-colored 3 - [/ 2-chloro-4-trifluoromethyl / phenoxy] benzoic acid which has separated out is filtered off and washed with water. Yield 81.6g, 75.3%, m.p .: 182-186 ° C. Beige powder.

Gross formula: C [deep] 14H [deep] 7ClF [deep] 3NO [deep] 5

Molecular weight: 361 / calculated /

The characteristic fragments of the mass spectrum:

m / e /r.i./ = 361/510 / = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 4COOH

344/190 / = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 4CO

316/130 / = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 4

137/1000 / = OC [low] 6H [low] 4COOH

The characteristic bands of the IR spectrum:

small Ny CO = 1685, small Ny as C-O-C = 1320, small Ny s C-O-C = 1130, small Ny as NO [deep] 2 = 1535 cm [high] -1. b / The 5 - [/ 2-chloro-4-trifluoromethyl-2-nitro / -phenoxy] -2-nitro-benzoic acid is obtained by nitrating the 3 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy ] benzoic acid.

6.2 g / 0.0171 mol / 3 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -benzoic acid are weighed into a two-necked flask equipped with a magnetic stirrer and dropping funnel and then in a mixture of 12 , 5 ml of dichloromethane and 7.6 ml of acetic anhydride dissolved. The nitrating acid / 5.5 ml, 0.08 mol, 65% nitric acid + 5.4 ml concentrated sulfuric acid / is added at a temperature between + 5 ° C and + 10 ° C with vigorous stirring. After the addition is complete, the reaction mixture is stirred for a further 3 hours at room temperature. The dichloromethane is filtered off and the residue is poured onto ice. The viscous oil obtained is dissolved in dichloromethane and extracted with an aqueous sodium hydroxide solution. The pH of the aqueous phase is adjusted to 1 with concentrated hydrochloric acid. A solid product is eliminated. 4.6 g of the compound mentioned in the title are obtained, yield: 65%.

F .: 79-81 ° C. Yellow crystals.

Gross formula: C [deep] 14H [deep] 6O [deep] 7N [deep] 2ClF [deep] 3

Molecular weight: 406 / calculated /

The characteristic fragments of the mass spectrum:

m / e / ri / = 406/530 / = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 3 / NO [deep] 2 / COOH

389/70 / = F [deep] 3C / Cl / NO [deep] 2 / C [deep] 6H [deep] 2

224/1000 / = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2

196/480 / = F [deep] 3C / Cl / C [deep] 6H [deep] 3OH

166/170 / = C [low] 6H [low] 4 / NO [low] 2 / COOH

In the [high] 1H-NMR spectrum, the H [low] 3 and H [low] 6 protons give a small delta [low] 3 = 8.128 and small delta [low] 6 = 7.975 singlet characters.

The H [low] 5 appears as a doublet due to the ortho linkage with a small delta [low] 5 = 7.875 ppm / d, J [low] 5, 6 = 8Hz /.

The signs of H [deep] 2 and H [deep] 6 overlap / small delta = 7.05 ppm /.

In the IR spectrum the small Ny CO appears at 1710 cm [high] -1.

The salts of 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitrobenzoic acid can be prepared as follows:

A solution of 6.1 g / 0.015 mol / of the 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / phenoxy] -2-nitro-benzoic acid prepared according to Example 1 in 30 ml of diethyl ether is a solution of 0 , 9 g / 0.015 mol / isopropylamine and 10 ml of diethyl ether were added. When the addition is complete, the salt separates out and is filtered off after the solution has cooled. Yield 5.0g, 70%.

F .: 203-208 ° C.

The sodium salt is prepared by adding an equimolar amount of solid sodium hydroxide. During the production of the ammonium salt, gaseous ammonia is passed into the ethereal solution until the heat development ceases. The allylammonium, ethanolammonium and diethyl-2-propynylammonium salts are prepared in a manner analogous to the preparation of the isopropylammonium salt using the corresponding amine.

The characteristic constants of the salts prepared in this way are summarized in Table I.

Table 1

Example Chemical name of the salt Yield F. ° C

No.

_______________________________________________________________________________________

1 / a Sodium-5 - [/ 2-chloro-4-tri- 82 248-252

fluoromethyl-5-nitro / -phenoxy] -

-2-nitro-benzoate

1 / b ammonium-5 - [/ 2-chloro-4-tri- 79 150-156

fluoromethyl-5-nitro / -phenoxy] -

-2-nitro-benzoate

1 / c isopropylammonium-5 - [/ 2- 72 203-208

-Chlor-4-trifluoromethyl-5-

-nitro / -phenoxy] -2-nitro-

benzoate

1 / d allylammonium-5 - [/ 2-chloro-4- 80 185-189

-trifluoromethyl-5-nitro / -

phenoxy] -2-nitro-benzoate

1 / e ethanolammonium-5 - [/ 2-chloro-95 40-45

-4-trifluoromethyl-5-nitro / - / hygrosco-

-phenoxy] -2-nitro-benzoate pisch /

1 / f diethyl-2-propynyl-ammonium 91 58-60

5 - [/ 2-chloro-4-trifluoromethyl-

-5-nitro / -phenoxy] -2-nitro-

benzoate

________________________________________________________________________________________

In the [high] 1H-NMR spectrum of the salts given in Table 1, the aromatic protons appear at the same chemical shift value. The H [deep] 3 and H [deep] 6 protons give a singlet sign at small delta [deep] 3 = 8.37 and small delta [deep] 6 = 8.25 ppm. The H [low] 5 appears as a doublet / small delta [low] 5 = 7.94 ppm / d, J [low] 5.6 = 9 Hz / because of the Orto link.

The characters of H [deep] 2 and H [deep] 6 overlap.

In the IR spectrum of the salts, the small Ny as CO [high] - [low] 2 gives a strong broad band at 1605 cm [high] -1 and the small Ny [low] s CO [high] - [low] 2 medium sharp band at 1350 cm [high] -1.

Example 2

5 - [/ 2-Trifluoromethyl-4-nitro / -phenoxy] -2-nitro-benzoic acid ethyl ester

/ Connection No. 2 /

a / In a two-necked round bottom flask are 10 g / 0.06 mol / 3-hydroxy-benzoic acid ethyl ester, 13.53 g / 0.06 mol / 2-chloro-5-nitrobenzotrifluoride and 8.3 g / 0.06 mol / potassium carbonate weighed out and the mixture is suspended in 100 ml of acetone. The reaction mixture is refluxed for 8 hours. After filtering off the potassium salt, the light red filtrate is evaporated and the residue is recrystallized. 15 g of the compound mentioned in the title are obtained, yield 70.4%. F .: 63 ° C.

Sand colored powdery product.

Gross formula: C [deep] 16H [deep] 12O [deep] 5NF [deep] 3

Molecular weight: 355 / calculated /

The characteristic fragments of the mass spectrum:

m / e /r.i./ = 355/680 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 4COOC [deep] 2H [deep] 5

341/280 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 4COOCH [deep] 3

327/300 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 4COOH

310/1000 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 4CO

The [high] 1H-NMR spectrum confirms the given structure:

small delta [deep] 3 = 8.5 / d, J [deep] 35 = 2Hz /, small delta [deep] 5 = 8.22 / dd, J [deep] 53 = 2 Hz, J [deep] 56 = 8Hz /, small delta [deep] 6 = 7.25, small delta [deep] 4 '= 7.92 / d, J [deep] 4'5' = 8Hz /, small delta [deep] 2 '= 7, 7, small delta [deep] 5 '= 7.5 / dd, J [deep] 5'4' = J [deep] 5'6 '= 8Hz /, small delta [deep] 6' = 6.85 / d , J [deep] 6'5 '= 8Hz /, small delta [deep] CH [deep] 2 = 4.325 / q, J = 7Hz /, small delta [deep] CH [deep] 3 = 1.325 ppm / t, J = 7Hz /.

b / 8.8 g / 0.025 mol / 3 - [/ 2-trifluoromethyl-4-nitro / -phenoxy] -benzoic acid ethyl ester are weighed into a two-necked round-bottomed flask equipped with an internal thermometer and magnetic stirrer, after which this ester is dissolved in 33.0 ml dichloromethane and 19.8 ml of acetic anhydride is dissolved. A mixture of 4.2 ml / 0.092 mol / 65% strength nitric acid and 4.2 ml of 98% strength sulfuric acid is added dropwise to the solution with external ice cooling. After the addition of the nitration mixture, the temperature rises to 10 ° C. During the addition, which takes 2 hours, the temperature of the solution is kept at 10-15 ° C. The reaction mixture is stirred for a further 3 hours at room temperature, a light yellow powder-like precipitate separating out.

After the dichloromethane has been distilled off, the residue is poured onto ice. A yellowish white precipitate is formed immediately, which is recrystallized from 60 ml of methanol. After the warm solution has cooled down, a powder-like crystalline product quickly separates out. 6.8 g of the compound mentioned in the title are obtained, yield 85.0%, mp .: 100-101 ° C. Snow-white powder-like product.

Gross formula: C [deep] 16H [deep] 11O [deep] 7N [deep] 2O [deep] 3

Molecular weight: 400 / calculated /

The most intense fragments of the mass spectrum are as follows:

m / e / ri / = 400/780 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 3 / NO [deep] 2 / COOC [ deep] 2H [deep] 5

372/380 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 3 / NO [deep] 2 / COOH

371/390 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 3 / NO [deep] 2 / COO

355/1000 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 3 / NO [deep] 2 / CO

280/370 / = F [deep] 3C / NO [deep] 2 / C [deep] 6H [deep] 3OC [deep] 6H [deep] 2CO

75/880 / = C [low] 6H [low] 3

The [high] 1H-NMR spectrum confirms the given structure:

small delta [deep] 5 = 8.375 / dd, J [deep] 56 = 8Hz /, J [deep] 53 = 2Hz /, small delta [deep] 5 '= 7.975 ppm / d, J [deep] 5'6' = 8Hz /, the other aromatic protons give complex multiplett, small delta [deep] CH [deep] 2 = 4.3 / q, J = 7Hz /, small delta [deep] CH [deep] 3 = 1.3 ppm / t, J = 7Hz /.

Example 3

5 - [/ 3-chloro-3-trifluoromethyl-2,6-dinitro / -phenoxy] -2-nitro-benzoic acid ethyl ester

/ Connection No. 3 /

a / In a two-necked round bottom flask, 5 g / 0.03 mol / 3-hydroxy-benzoic acid ethyl ester and 4.15 g / 0.03 mol / anhydrous potassium carbonate are suspended in 30 ml of acetone under nitrogen, whereupon 18.3 g / 0.06 mol / 2,4-dichloro-3,5-dinitro-benzotrifluoride, dissolved in 20 ml of acetone, are added. The reaction mixture is stirred for an additional 20 hours at room temperature. The precipitated potassium chloride is filtered and the solution is concentrated. The residue is made from 60 ml

Recrystallized methanol. A yellowish-white powder-like product which turns yellow in the air is obtained. Yield 5.6g, 43%. F .: 86-89 ° C. A yellowish white powder-like product.

Gross formula: C [deep] 16H [deep] 10O [deep] 7N [deep] 2ClF [deep] 3

Molecular weight: 434.5 / calculated /

The mass spectrum shows that the molecule contains one chlorine atom; the isotopes with the mass numbers 35 and 37 result in double peaks with the m / e values 434/436 [389/391].

m / e / ri / = 434/436 [740/280] = F [deep] 3C / Cl // NO [deep] 2 / [deep] 2C [deep] 6HOC [deep] 6COOC [deep] 2H [deep] 5

389/391 [950/330] = F [deep] 3C / Cl // NO [deep] 2 / [deep] 2HOC [deep] 6H [deep] 4CO

165/800 / = OC [deep] 6H [deep] 4COOC [deep] 2H [deep] 5

137/520 / = OC [low] 6H [low] 5COOH

212/1000 / = C [low] 6H [low] 5COO

The [high] 1 l-NMR recording confirms the stated structure:

small delta [deep] 5 = 8.46, small delta [deep] 4 '= 7.8 / dd, J [deep] 4'5' = 7Hz, J [deep] 4'2 '= 1.5 Hz / , small delta [deep] 6 '= 7.06 / dd, J [deep] 6'5' = 8 Hz, J [deep] 6'2 '= 2Hz /, small delta [deep] CH [deep] 2 = 4.275 / q, J = 7 Hz /, small delta [low] CH [low] 3 = 1.3 ppm / t, J = 7 Hz /.

The NO [deep] 2 band of the IR micrograph shows the presence of more than one NO [deep] 2 group. The asymmetrical and symmetrical stretching vibrations of the C-O-C bond are most intense at the wave numbers of 1150 and 1300 cm [high] -1.

b / The nitration is carried out under the reaction conditions and molar ratios given in Example 2. When working up the reaction mixture, the residue poured onto ice solidifies immediately and a yellowish-white substance separates from, which is recrystallized from 60 ml of methanol. 6.8 g of the compound mentioned in the title are obtained, yield 83.5%. F .: 95-97 ° C. Snow-white powdery product.

Gross formula: C [deep] 16H [deep] 9O [deep] 9N [deep] 3ClF [deep] 3

Molecular weight: 479.5 / calculated /

The mass spectrum confirms the presence of a chlorine atom. The intensity ratios correspond to the abundance of the isotopes.

The main fragments are the following:

m / e / ri / = 479/481 [500/160] = F [deep] 3C / Cl // NO [deep] 2 / [deep] 2C [deep] 6HOC [deep] 6H [deep] 3 / NO [ low] 2 / COOC [low] 2H [low] 5

451/453 [310/120] = F [deep] 3C / Cl // NO [deep] 2 / [deep] 2C [deep] 6HOC [deep] 6H [deep] 3 / NO [deep] 2 / COOH

434/436 [1000/340] = F [deep] 3C / Cl / NO [deep] 2 / [deep] 2C [deep] 6HOC [deep] 6H [deep] 3 / NO [deep] 2 / CO

165/660 / = OC [deep] 6H [deep] 4COOC [deep] 2H [deep] 2

The [high] 1H-NMR recording confirms the stated structure:

small delta [deep] 5 = 8.55, small delta [deep] 5 '= 7.9 / d, J [deep] 5'6' = 8 Hz /, small delta [deep] 2 '= 7.1 / d, J [low] 2'6 '= 1.5 Hz /, small delta [low] 6' = 7.025 / dd, J [low] 7'5 '= 8 Hz, J [low] 6'2' = 1.5 Hz /, small delta [low] CH [low] 2 = 4.275 / q, J = 7 Hz /, small delta [low] CH [low] 3 = 1.25 ppm / t, J = 7 Hz / .

The IR image confirms the presence of more than one NO [deep] 2 group. In the nitrided derivative, the small Ny C-O-C bands occur at higher wavenumber values, namely at 1150 and 1350 cm [high] -1.

Example 4

5 - [/ 2-Chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid ethyl ester

/ Connection No. 4 /

a / The procedure is as in Example 3, as described for the preparation of the ethyl 3 - [/ 2-chloro-4-trifluoromethyl-2,6-dinitro / phenoxy] benzoate. The product is dissolved in 50 ml of methanol and the solution is cooled. A little methanol is layered on top of the solution. After stirring, a yellowish-white powder-like precipitate separates out, which is washed on the filter with a little methanol. Yield 6.0g, 51.3%.

F .: 64-65 ° C. Yellowish white powder.

Gross formula: C [deep] 16H [deep] 11O [deep] 5NClF [deep] 3

Molecular weight: 389.5 / calculated /

It can be seen from the mass spectrum that the compound contains chlorine atom, because the two largest fragments give a double symbol according to the ratio of the [high] 35Cl and [high] 37Cl isotopes.

m / e / ri / = 389/391 [750/260] = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 4COOC [deep ] 2H [deep] 5

344/346 [870/280] = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 4CO

165/550 / = OC [deep] 6H [deep] 4COOC [deep] 2H [deep] 5

121/1000 / = C [low] 6H [low] 5COO

The [high] 1H-NMR recording confirms the stated structure:

small delta [low] 6 = 8.07 / d, J [low] 63 = 1 Hz /, small delta [low] 3 = 8.9 / d, J [low] 36 = 1 Hz /, small delta [low ] 4 '= 8 Hz /, small delta [low] 6' = 6.95 / J [low] 6'5 '= 7 Hz /, small delta [low] CH [low] 2 = 4.25 / q, J = 7 Hz /, small delta [low] CH [low] 3 = 1.3 ppm / t, J = 7 Hz /. b / The procedure is as in Example 2, with the difference that instead of 3 - [/ 2-trifluoromethyl-4-nitro / -phenoxy] -benzoic acid ethyl ester, 3 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -benzoic acid ethyl ester nitrated. The reaction mixture is poured onto ice. The excreted yellow substance solidifies on standing and can be broken easily. After recrystallization from 50 ml of methanol, 7.15 g of the compound named in the title are obtained, yield 82.2%. F .: 83-84 ° C. Yellowish white powdery product.

Gross formula: C [deep] 16H [deep] 10O [deep] 7ClF [deep] 3

Molecular weight: 434.5 / calculated /

All fragments of the mass spectrum contain chlorine. The characteristic fragments are as follows:

m / e / ri / = 434/436 [580/200] = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 3 / NO [low] 2 / COOC [low] 2H [low] 5

406/408 [150/50] = F [deep] 3C / Cl // NO [deep] 2 / [deep] 2C [deep] 6H [deep] 2OC [deep] 6H [deep] 3 / NO [deep] 2 / COOH

389/391 [450/150] = F [deep] 3C / Cl // NO [deep] 2 / C [deep] 6H [deep] 2OC [deep] 6H [deep] 3 / NO [deep] 2 / CO

224/226 [1000/350] = F [deep] 3C / Cl / NO [deep] 2 / C [deep] 6H [deep] 2

194/380 / = F [deep] 3C / Cl / C [deep] 6H [deep] 2O

166/260 / = C [low] 6H [low] 3 / NO [low] 2 / COOH

The amplification of the small Ny NO [deep] 2 band can be seen on the IR image. The small Ny CO band was shifted because of the nitriding in the direction of the higher wave number, namely from 1705 cm [high] -1 to 1725 cm [high] -1.

B. Examples of preparation of the preparations

Example 5

A suspension concentrate / SC / is produced with the following composition:

Component amount,%

________________________________________________________________________________

Active ingredient / Compound No. 2 / 50.0

Ethylene glycol 8.0

Nonylphenyl poly / glycol ether / / 10 EO / 5.0

Polysaccharide 0.1

Silicone oil 1.5

Water 35.4

Example 6

A wettable powder / WP / of the following composition is produced:

Component amount,%

________________________________________________________________________________

Active ingredient / Compound No. 1 / 90.0

Highly disperse silica 5.0

Dispersant 5.0

Example 7

Granules of the following composition are produced:

Component amount,%

_________________________________________________________________________________

Active ingredient / Compound No. 3 / 5.0

Ground limestone 69.0

/ Component / / amount,% /

Ethylene glycol 3.0

Highly disperse silica 5.0

Sodium lignosulfonate 3.0

Water 13.5

Example 8

A spray / dry flowable / the following composition is produced:

Component amount,%

_________________________________________________________________________________

Active ingredient / Compound No. 2 / 80.0

Sodium lauril sulfate 2.0

Sodium lignosulfonate 7.0

Water 3.0

Kaolin 8.0

Example 9

A water-soluble liquid concentrate / WSC / with the following composition is produced:

Component amount,%

__________________________________________________________________________________

Active ingredient / Compound No. 1 / d / 30.0

Ethylene glycol 5.0

Nonylphenyl poly / glycol ether / / EO = 10; 2.0

e.g. Arkopal N-100 /

ion exchanged water 63.0

Example 10

An emulsifiable concentrate / EC / with the following composition is produced:

Component amount,%

__________________________________________________________________________________

Active ingredient / Compound No. 2 / 40.0

Xylene 12.0

Cyclohexanone 20.0

Isophorone 20.0

Poly / oxyethylene / sorbitan monooleate 5.0

Nonylphenyl poly / glycol ether / / EO = 10 / 3.0

Example 11

Seed foil

a / 80 g RHODOVIOL 4/125 P polyvinyl alcohol / the viscosity of the 4% aqueous solution is 4 cP at 20 ° C; Degree of hydrolysis = 89 mol% / are added to 615 g of warm / 60 ° C. / water with stirring. After dissolution, 20 g RHODOVIOL 30/20 m polyvinyl alcohol / the viscosity of the 4% aqueous solution is 30 cP at 20 ° C; Degree of hydrolysis = 98 mol% / and 20 g of glycerol added. The mixture is vigorously stirred until a homogeneous solution is formed. After standing for 24 hours, the bubbles escape from the solution. The solution is applied with a doctor blade by pouring in the form of a 0.50 mm thick layer on a glass plate and dried at room temperature. The film obtained in this way peeled off the glass plate, the thickness was 0.05-0.06 mm. The slide is easy to treat.

b / The procedure is as in paragraph a / and a solution of similar composition suitable for the production of films is produced. A suspension of 0.120 g of compound no. 6 / active ingredient / in 5 ml of water is added to the solution. After removing the bubbles, a film is cast which is dried.

The film obtained is similar to the film produced in accordance with paragraph a /, but contains 1000 ppm of the active ingredient.

c / The procedure is as in paragraph b / with the difference that a suspension of 0.0120 g of compound no. 3 / active ingredient / in 5 ml of water is mixed with the solution. The active ingredient content of the film obtained is 100 ppm.

d / The procedure is as indicated above, with the difference that another compound according to the invention is used as the active ingredient.

C. Biological examples

Example 12

Determination of the fungicidal effectiveness

The fungicidal effectiveness of the active ingredients is determined using the poisoned agar plate method. The essence of the method is that the preparations containing the tested active ingredient - depending on the active ingredient content - as much water and then potato agar nutrients containing 2% dextrose soil adds that the preparation and the nutrient medium together produce the desired active ingredient concentrations.

The nutrient medium poisoned in the appropriate concentration is poured into Petri dishes and allowed to solidify. The mycelia slices of the same size cut from the pure culture of the test fungi are inoculated. The Petri dishes are incubated for 3-7 days depending on the test fungi. The experiment was evaluated on the basis of the fungus growth in such a way that the diameter of the column was measured / mm / and expressed in% of the untreated control. The diameter of the control column is regarded as "protection value = 0%" and the protection values obtained with different concentrations of the active ingredient are determined accordingly / in% /. In the tests, the active substance content of the poisoned nutrient media was 500, 100, 20 and 4 ppm.

The following fungi are used: Fusarium graminearum, Stemphylium radicinum and Aspergillus niger.

The results obtained are compared with the control / Captan / and summarized in Tables 2 and 3. The test results show that the new active ingredients according to the invention are at least equivalent to the known captan - in most cases even significantly superior.

Table 2

Effectiveness, in protection value%

Table 3

Effectiveness, in protection value%

Claims (4)

1. Composition for combating fungi pests of useful plants, characterized in that it is used as active ingredient in an amount of 0.0001-96% by weight of 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy ] -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 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 and one or more solid and / or liquid carriers and optionally surface-active agents and / or dispersants - contains. 2. Composition according to claim 1, characterized in that it is the sodium, ammonium, isopropylammonium or allylammonium salt of 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro- contains benzoic acid. 3. A method for controlling fungi pests of useful plants, characterized in that the soil, the seeds of the useful plant, the plants or a part thereof as active ingredient in an amount of 0.0001-20 wt .-% - advantageously 0, 01-5% by weight - with 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid or a salt or the ethyl ester thereof; or 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 treated. 4. The method according to claim 3, characterized in that the active ingredient the sodium, ammonium, isopropylammonium or allylammonium salt of 5 - [/ 2-chloro-4-trifluoromethyl-5-nitro / -phenoxy] -2-nitro-benzoic acid is used.