HU193194B - Fungicide compositions containing phenoxy-benzaldehyde derivatives as active substances and process for preparing the active substances - Google Patents

Abstract

Fungicidal agents contain as active ingredient new phenoxybenzaldehyde derivatives of the general formula I in which R 1 and R 3 are trifluoromethyl or nitro, where R 1 and R 3 can not simultaneously be the same group, R 2 is hydrogen or a 3-formylphenoxy radical, X Is hydrogen or chlorine and Y is hydrogen or nitro.

Description

The present invention relates to a phenoxybenzaldehyde derivative (I) of the formula (I)

R 1 and R 3 are (trifluoromethyl) or nitro, with the proviso that R 1 and R ₃ are different from each other,

R ₂ is hydrogen or 3-formylphenoxy,

X is hydrogen or chlorine,

Y is a fungicidal composition containing a hydrogen atom or a nitro group; and a process for preparing a new phenoxybenzaldehyde derivative of formula (I) wherein R 1, R 2, R 3, X and Y are as defined above, provided that when R 1 is nitro and R ₃ is trifluoromethyl, at least one of R ₂ , X and Y is other than hydrogen.

Substituted phenoxybenzene derivatives (formerly known as diphenyl ethers) have been known for over twenty years as herbicides, especially in rice, cotton, soybean crops. This family of compounds is described in detail in pages 73-80 and 401-407 of R. Wegler, Chemie dér Pflanzenschutz- und Schadlingsbekampfungsmittel Bánd 5 (Springer-Verlag Berlin Heidelberg NewYork 1977). Among the diphenyl ether derivatives, the following compounds have particularly good herbicidal activity:

- 2-nitro-1- (4-nitrophenoxy) -4-trifluoromethylbenzene (fluororedifen), - 2-chloro-1- (4-nitrophenoxy) -4- (trifluoro) methyl) benzene (nitrofluorophene), - 2-chloro-1- (3-ethoxy-4-nitrophenoxy) -4- (trifluoromethyl) benzene (oxyfluorophene), - sodium 5 - [2-chloro-4- (trifluoromethyl) phenoxy-2-nitrobenzoate (acifluorophenic sodium) and - ethyl 5- [2-chloro-4- (trifluoromethyl) phenoxy] 2- nitrobenzoate (acifluorophenethyl).

(USP 3 798 276, USP 4 031131, USP

164 408, CB-PS 1 390 295, DE-OS 23 33 848) The compounds which are closest to the present invention but which are structurally different, such as herbicides, are disclosed in U.S. Patent No. 4,306,900. United States Patent No. 3,617,795; It can be found in the disclosure document in the Federal Republic of Germany. The fungicidal activity of the same known compounds is disclosed in Hungarian Patent Publication No. 190,222.

In our experiments on new phenoxybenzaldehyde derivatives, we have found that our compounds are excellent fungicides.

The present invention relates to a fungicidal composition comprising from 0.001% to 95% by weight of the phenoxy-benzaldehyde derivative (s) of the formula (I) in which

R 1 and R ₃ are (trifluoromethyl) - or nit 2, with the proviso that R 1 and R ₃ are different from each other,

R2 is hydrogen or 3-formylphenoxy,

X is hydrogen or chlorine,

Y is a hydrogen atom or a nitro group with one or more solid and / or liquid carriers, preferably ground minerals or inert organic solvents, and optionally surfactant (s), preferably anionic or nonionic emulsifying and / or dispersing agents.

The present invention also relates to the preparation of new phenoxy benzaldehyde derivatives of formula (I): - wherein R, R _2, R 3, and X

Y is as defined above, with the proviso that when R 1 is nitro and R ₃ is trifluoromethyl, at least one of R ₂ , X and Y is other than hydrogen.

The novel phenoxybenzaldehyde derivatives of the present invention may be prepared by any of the known methods. so for example

a) by the classic Ullman ether synthesis, whereby the reaction of the corresponding phenol derivative (the alkali metal salt of the trifluoromethylphenol derivative with 3-halobenzaldehyde or 2-nitro-5-halobenzaldehyde) can also be carried out, reacting the alkali metal salt of 3-hydroxybenzaldehyde or m-cresol with the appropriately substituted benzotrifluoride derivative in the presence of m-cresol to hydrolyze the benzaldehyde to obtain the corresponding carboxylic acid or mild halogenation of the toluene; Partial reduction of the carboxylic acid ester or partial oxidation of the aminomethyl, chloromethyl and hydroxymethyl derivatives also yields the corresponding aldehydes, or the hydrolysis of the imine formed by the partial reduction of the nitrile to form the alkali metal salt of the formyl group in the presence of a suitable catalyst Views reacted benzene derivative.

b) shorter reaction times and higher yields can be achieved using dipolar aprotic solvents (e.g. dimethylformamide, dimethylacetamide, sulfolane, dimethylsulfoxide, acetone, etc.). In this case, the reaction proceeds without a catalyst by selecting the appropriate boiling point solvent,

c) in the SN2-type etherification reaction, the phenolate anion and a neutral molecule (halogenated benzene) react. To judge the role of the incoming nucleophilic group

-2193194 nucleophilic force and steric factors should be considered. The quality of the group to be replaced (usually halogen) and the activating action of the substituents on the aromatic ring also play an important role in determining the reaction rate. There are several preferred process variants for the preparation of the novel substituted phenoxy-2-nitrobenzaldehydes of the present invention, such as, for example, direct coupling of the substituted halobenzotrifluoride with 4-nitrophenol, e.g. in the presence of an alkali metal hydroxide or alkali metal carbonate or an acid acceptor; or - coupling of the substituted halobenzotrifluoride with phenol under similar reaction conditions and subsequent nitration of the coupled "intermediate" (which itself is a good fungicide) by a known nitration process.

The compounds (active ingredients) of the present invention are formulated into formulations known in the art, such as wettable spray powders (WP), suspension concentrates (SC), emulsion concentrates (EC), optionally ultra low volume (ULV) or film, preferably core film, and the like. forms. In these formulations, the active compounds or mixtures thereof are admixed with solid or liquid inert carriers, diluents and, optionally, other excipients.

Such excipients may be, for example, surfactants such as wetting agents, suspending, dispersing, emulsifying, anti-caking, anti-adhering, anti-seizing, potentiators, or substances that maintain or enhance the biological effect, antifoams, etc.

Suitable solid carriers and diluents include inactive minerals such as various kaolins, porcelain soils, attapulgite, montmorillonite, mica, pyrophyllite, bentonite, diatomaceous earth or highly dispersed synthetic silicic acid, calcium calcium, oxide, dolomite, gypsum, tricalcium phosphate, Fuller shingles, etc. Suitable solid diluents and carriers include tobacco leaf meals, wood flour, and the like.

Suitable liquid carriers, diluents and solvents include water, organic and / or aqueous organic solvent mixtures, such as methanol, ethanol, n- and i-propanol, diacetone alcohol, benzyl alcohol; glycols such as ethylene, diethylene, triethylene glycol, propylene glycol, esters thereof such as methylcellosolve, butyldiglycol; ketones such as dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .; esters such as ethyl acetate, n- and i-propyl acetate, n- and i-butyl acetate, amyl acetate, isopropyl myristate, dioctyl phthalate, dihexyl phthalate, etc .; aromatic, aliphatic, alicyclic hydrocarbons such as paraffinic hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetralin, decalin; mixtures of alkyl biphenols; chlorinated hydrocarbons such as trichloroethane, dichloromethane, perchlorethylene, dichloropropane, chlorobenzene, etc .; lactones such as γ-butyrolactone, etc .; lactams such as N-methylpyrrolidone, N-cyclohexylpyrrolidone; acid amides such as dimethylformamide, etc .; vegetable and animal oils such as sunflower seed, linseed, rapeseed, olive, soybean, castor and sperm oils, etc.

Suitable wetting, dispersing and emulsifying agents, adhesives, anti-aggregating agents, anti-lump agents, can be ionic or nonionic. They may be ionic; salts of various saturated and unsaturated carboxylic acids; sulfonates of aliphatic, aromatic, aliphatic-aromatic hydrocarbons; sulfates of alkyl, aryl, aralkyl alcohols; sulfonates of acids, alkyl, aryl, aralkyl esters, ethers; sulfonates of the condensation products of phenol, cresol, naphthalene; sulfated vegetable and animal oils; salts of alkyl, aryl, aralkyl phosphate esters and the compounds listed above with alkali and alkaline earth metals or organic bases such as various amines, alkanolamines. For example, sodium lauryl sulfate, sodium 2-ethylhexyl sulfate; sodium, ethanolamine, diethanolamine, triethanolamine, isopropylamine salts of dodecylbenzenesulfonic acid; sodium mono- and diisopropyl-naphthalene sulfonate; sodium salt of naphthalenesulfonic acid; sodium diisooctyl sulfosuccinate, sodium xylenesulfonate; the sodium or calcium salt of petroleum sulfonic acid; lubricating soaps; potassium, sodium, calcium, aluminum, magnesium stearate, etc. Phosphate esters may be polyglycol esters of phosphated alkyl phenols or fatty alcohols, and may be partially or wholly inactivated with the aforementioned cations or organic bases. Similarly, anionic surfactants include disodium N-octadecyl sulfosuccinate, sodium N-oleyl N-methyl tauride, etc .; and various lignin sulfonates.

Suitable nonionic wetting, dispersing and emulsifying agents, etc. ethers of ethylene oxide with alcohols having from 10 to 20 carbon atoms, such as; stearyl polyoxyoxyethylene, oleyl polyoxyoxyethylene; ethers with alkyl phenols such as t-butyl, octyl, polyglycol ethers with nonyl phenols; esters of various organic acids such as 3

-3193194 esters of stearic acid and myristic acid with polyethylene glycol or polyethylene glycol oleate, etc .; ethylene oxide, propylene oxide block polymers; partial esters of fatty acids with oleic acids, such as esters of sorbitol with oleic or stearic acids, etc .; or condensation products of such compounds with ethylene oxide; tertiary glycols such as 3,6-dimethyl-4-octin-3,6-diol or 4,7-dimethyl-5-decine-4.7 diols; polyethylene glycol thioethers such as polyethylene glycol ether of dodecyl nercerkan, etc. Suitable tackifiers include alkaline earth metal soaps, sulfuric acid ester salts, natural and artificial water-soluble macromolecules such as casein, starch, vegetable gums, arabic gum, cellulose ethers, methyl cellulose , hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, and the like. Suitable antifoam agents include low molecular weight polyoxyethylene, polyoxypropylene block polymerizers; octyl, nonyl, phenyl polyoxyethylene (ethylene oxide units> 5); long chain alcohols such as octyl alcohol, etc .; special silicone oils, etc.

By using a suitable additive, the formulated compositions can be colloid chemically compatible with various fertilizer systems. If necessary, known pesticides and / or nutrients are used as ingredients in the formulation.

Wettable sprayable powders (WPs) may be prepared, for example, by mixing the active ingredient (s) as well as the excipient (s), surfactant (s), and then grinding and homogenizing. In the case of a liquid surfactant, it is also possible to apply the liquid surfactant to the solid organic or inorganic diluent (s), or to a powder mixture containing the solid, for example by spraying. The same applies to liquid active ingredients. In the case of a liquid surfactant, it is also possible to suspend the pre-ground solid components in an organic solvent containing the liquid surfactant (s). This suspension is dried, for example, by spraying. In this way, the surfactant is applied to the surface of the solid active ingredient and the solid diluent.

A self-emulsifying liquid, so-called emulsion-forming concentrate (EC), suitable for the production of an aqueous dispersion medium emulsion, may be prepared by dissolving the active ingredient or mixture thereof in a water-immiscible solvent with one of the surfactants and emulsifiers described above. The emulsion-forming concentrate thus obtained, either voluntarily with water or for 4 to 6 small mechanical influences, forms a spray-juice emulsion which does not change even after prolonged standing.

A water-miscible solution concentrate (SL) can be prepared by preparing an aqueous and / or water-miscible solvent solution of the active ingredient and the appropriate water-soluble excipients. Dilution with water produces the desired concentration of spray liquid.

Aqueous concentrates of the active ingredient can also be dispersed in a water immiscible liquid by selecting a suitable emulsifier to form an invert emulsion. Thus, by appropriate choice of solvent and surfactants, compositions can be prepared which, when mixed with water or a water immiscible liquid, produce systems, even molecularly dispersed, that do not change over time.

To prepare a suspension concentrate (SC) in a mixture of water (preferably deionized) and an antifreeze component (preferably ethylene glycol or glycerol), the wetting and dispersing agents are removed by heating, if necessary. Solid (powdered or crystalline) active ingredient (s) is added to this solution while stirring continuously, and if necessary, synthetic silica is added as an anticaking component. The resulting slurry fluid system (slurry) is wet milled using wet mill equipment (e.g., a closed Dyno mill) to the desired particle size, which is generally max. It has a particle diameter of 5 micrometers, followed by grinding, if necessary, with an antifoam component or a polysaccharide as a thickening component during homogenization. Alternatively, the mixing order of the components may be changed or other components (e.g., dye, etc.) may be added as needed. In addition to the solid active ingredient, liquid, water-immiscible or water-miscible agents may also be used as combination partners. Low melting point solids may also be incorporated in the form of a bulk without an emulsifier or in admixture with an emulsifier.

ULV formulations may be prepared in a manner similar to EC agents (sometimes SC agents).

Granules (G) for direct use can be prepared by extrusion. by layering using an already particulate carrier (such as limestone ground) or by absorbing a liquid component with a sorption capacity carrier.

Spray granulates (WG) can be prepared from WP and / or SC from some agglomeration

-4193194 technology, for example using binder in a draining pan.

Dilution with water or an inhalable solid diluent, known in the art, produces a spray or powder for agricultural use which generally has an active ingredient content of less than 5% by weight, preferably from 1 to 0.01% by weight. Alternatively, the spray broths of the various single-ingredient formulations may be combined prior to use.

A preferred embodiment of the solid fungicidal compositions useful in the present invention is the seed film. It is known that in horticulture, but also in other agricultural practices, the seeds are wrapped in a water-soluble film instead of hand-sowing (planting) to facilitate sowing of seeds and to provide uniform seed and row spacing seeds are planted in the soil. The film may be any water soluble material, such as polyvinyl alcohol, etc., that is in contact with the seeds. it may only be required not to damage the seeds and to disintegrate and, if necessary, dissolve in the soil under the influence of moisture. The seed film may contain the active compounds of the invention incorporated into the film, or the seeds treated with the active compounds of the present invention may be incorporated into the film.

The most common chemical pest control methods for the control of plant pathogens, the prevention of fungal infections are: dressing, spraying and dusting. The composition containing the fungicidal active ingredient - dressing, spraying agent, dusting agent, etc. - naturally, it must be applied to that part of the host plant or its environment where the source of infection occurs or from where the pathogen spreads.

For the production of non-infectious seed, seedlings are used for seed treatment of fungi infecting the soil). Seeds and seedlings are mainly endangered by moldy conidium fungi. By way of example, maize, which fungi that cause toxic fusariosis, Fusarium graminearum and Fusarium moniliforme, as well as Nigrospora oryzae fungi, which cause dry rot in nigrospores, are propagated by the seed itself.

In addition, the fungus seed can be attacked by many other fungi, e.g. members of the Rhizoctonia, Penicillium, Helminthosporium genus. All of these pathogens are so-called. moldy conidium fungus. Several known fungicides can be used to control them, e.g. with 5 - {[2,6-dichloro-4- (trifluoromethyl)] -phenoxy} -2-nitrobenzaldehyde, of which about 0.5 to 0.6 kg is used to disinfect 1 ton of seed.

Plant stock treatment eg. spraying or dusting is applied against fungi endangering the foliage and fruit (fruit) of the plant. An example is apple, whose monilia is caused by the fungus Spilocea pomi (Fusicladium dendriticum), the monilia of which is Monilia fructige25 na. Or e.g. gray rot of grapes is caused by Botrytis cinerea. These fungal species are also moldy conidium fungi and from the already mentioned 5 - {[2,6-dichloro-4- (trifluoromethyl)] -phenoxy} -2-nitrobenzaldehyde, ca. 120 g are used in 100 l of spray broth to spray these fungi.

The importance of mold-like conidium fungi is emphasized because the compounds of the invention are primarily effective against them.

These fungi represent Monilialis order of the Deuteromycetes class and the vast majority ⁴⁰ GUK tömlőspórás fungi (ascomycetes class) vegetative multiplying forms. In particular, three of their families cause great damage to crop production.

The following is a list of the most important genera in each of these families, as well as a reference to a particular species.

salad:

genus: species: Monilia (e.g. · M, Aspergillus (e.g. A, Penicillium (e.g. P. Botrytis (e.g. B Verticillium (e.g. v TrichothecLum (e.g. T

Cercosporella {pl, C

Fructigena - almamonilia) niger - black soot) crustaceum - green brush mold) cinerea - gray mold) albo-atrum - infectious wilt eg paprika) roseum - pink fruit mold) herpotrichoides - stem fungus)

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(b) Dematiaceae family:

genus: species:

Thielaviopsis (e.g. T. Nigro spore (e.g. N, Spilocea (e.g. s.

Cladosporium (e.g. c. HeImintho sporium (e.g. H. Gercospora (e.g., C. Maria Alte (e.g., A. Steraphylium (e.g. s.

basicola - black root rot) oryzae - eg. corn stalk rot) pomi synonym Fusicladium dendriticum - apple rotting) fulvum - brown mildew) turcicum - heminthosporium wilt) beticola - beet leaf clover) solani - potato alternative) radicinum - beet root rot)

(c) Tuberculariaceae family:

genus: species:

Fusarium (eg F, gratninearura - cereal fusarium and x

F, various forms of oxysporum - e.g. potato tracheomycosis)

As mentioned above, the fungi in question also have sexual hose shapes, e.g. the shape of Spilocea pomi is known as Venturia ₄₅ inaequalis, also known as Endostigme inaequalis.

Of course, mold-like conidium fungi have thousands of species of dangerous pathogens, and only a few genera have been mentioned as examples. However, they are characterized by the fact that a contact fungicide effective against any of them is effective against all of the fungi listed, although there are differences in sensitivity, but they are not very significant. In the following, the efficacy data for Apergillus niger and Botrytis cinerea, and then for the 17 conidium species, are thus approx. apply to the whole Moniliales. Because these studies were conducted in vitro with the standard 5 - {[2,6-dichloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzaldehyde, the efficacy values in ppm and mg / l respectively were compared. they are given, but proportionally they also apply to outdoor conditions.

The invention is illustrated by the following examples, without limiting the scope of the invention.

Examples of active ingredient preparation:

Example 1

3 - {[5-Chloro-4- (trifluoromethyl) -2-nitro] phenoxy) -benzaldehyde (active ingredient # 1) in anhydrous acetone (7.8 g, 0.03 mol)

2,4-Dichloro-5-nitrobenzotrifluoride, 4.4 g (0.036 mol; 20% molar) of 3-hydroxybenzaldehyde and 4.97 g (0.036 mol) of anhydrous potassium carbonate are added and the suspension is maintained for 16 hours. stirring at room temperature. The reaction mixture was filtered and the filtrate was filtered off with suction under acetone. The oily residue was dissolved in isopropanol at reflux temperature and then slowly cooled with stirring to give a crystalline product.

Yield: 8.0 g, 77%.

Mp 80-83 ° C.

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Color and shape of the product: beige crystal, total formula: C14H7O4NCIF3, molecular weight: 345 (calculated).

The mass spectrum of the product is characterized by the following fragments: m / e (r.i.) =

345 (800) = F ₃ C (Cl) (NO ₂ ) C ₆ H ₂ OC ₆ H ₄ CHO 300 (300) = F ₃ C (C 1) C ₆ H ₃ OC ₆ H ₄ CHO 328 (150) = F ₃ C (C1) (NO ₂₎ C ₆ H ₆ OC ₂ H4c 224 (1000) = F ₃ C (C1) (NO ₂₎ C ₆ H ₂ 121 (620) = OC ₆ H4CHO

In the Ή-NMR spectrum, it is difficult to assign each proton to the appropriate signal due to the overlapping of the different signals. The formyl proton of the coupled compound appears at 9.92 ppm. The IR spectrum of the formyl group at 1680 cm-1 shows the μ CO band of the formyl group, at 2830 and 2730 cm ^-1 the pCH band of the formyl group.

Example 2

3 - {[4- (Trifluoromethyl) -2,6-dinitro] phenoxy} benzaldehyde (Compound No. 2)

All proceed as in Example 1, except that 3,5-dinitro-4-chlorobenzotrifluoride is used in place of 2,4-dichloro-5-nitrobenzotrifluoride.

Yield: 9.5 g, 89%.

130-131 ° C.

Color and shape of the product: yellow crystal, total formula: C 14 H ₇ O ₆ N ₂ F ₃ , molecular weight: 356 (calculated).

Typical fragments found in the mass spectrum of the product are as follows:

m / e (r.i.) -

356 (870) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H ₄ CHO 337 (100) = F ₂ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H ₄ CHO

235 (180) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂

121 (1000) - OC ₆ H ₄ CHO

In the '1 H-NMR spectrum, the two protons between the trifluoromethyl and nitro groups appear at an appropriate ratio of 8.42 ppm and formylproton at 9.85 ppm.

In the IR spectrum, the pCO (1685 cm ^-1 ) and μ CH vibrations (2830-, 2940 ~ ') of the formyl group can be clearly identified.

Example 3

3 - {[2-Trifluoromethyl) -4,6-dinitro] phenoxy} benzaldehyde (active ingredient # 3)

All proceed as in Example 2, except that 2-chloro-3,5-dinitrobenzotrifluoride is used in place of 2,4-dichloro-5-nitrobenzene trifluoride.

Yield: 8.1 g, 76%.

Mp 104 ° C.

Color and shape of the product: light yellow crystal, total formula: Ct ₄ H ₇ O ₆ N ₂ F ₃ , molecular weight: 356 (calculated).

Characteristic fragments of the product mass spectrum are: m / e (r.i.) =

356 (880) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H; CHO

235 (570) = F ₃ C (NO ₂ ) C ₆ H ₂ 121 (1000) = οο ₆ η ₄ οηο

In the Ή-NMR spectra, the signal of the trifluoromethyl and the protons between the nitro groups and the nitro groups can be expected at different chemical shifts with well-recognized meta-coupling. The δ value of formylproton = 9.85 ppm is consistent with previous findings.

The IR spectrum of the formyl group shows the CO band at 1695 cm ^- ', and the CH band at 2750 cm - 2855 cm - 1.

Example 4

2,4-Bis (3-formylphenoxy) -1- (trifluoromethyl) -3,5-dinitrobenzene (active ingredient # 4).

3.66 g (0.03 mol) of 3-hydroxybenzaldehyde, 5.06 g (0.0175 mol of 10% molar excess) of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 4 ml of anhydrous acetone and Anhydrous potassium carbonate (55 g, 0.033 mol; 10% molar excess) was added and the reaction mixture was stirred at room temperature for 6 hours, then allowed to stand for 1 day. The suspension is filtered, the precipitate is washed with acetone, and the solvent is evaporated off from the acetone filtrate under a water jet vacuum. The residue was dissolved in hot isopropanol (60 mL) and slowly cooled to give a crystalline product.

Yield: 5.3 g, 85%.

M.p. 137-138 ° C.

Color and shape of the product: light yellow crystal, total formula: C ₂ H ₁₁ O ₈ N ₂ F ₃ , molecular weight: 476 (calculated).

The mass spectrum of the product identifies only the double-linked compound:

m / e (r.i.) =

476 (560) = F ₃ C (NO ₂ ) ₂ C ₆ H 4 (CHO) ₂

459 (1000) = F ₃ C (NO _{2) 2} C ₆ H (OC ₆ H4CHO) OC ₆ H ₄ C

367 (220) = F ₃ CC ₆ H (OC ₆ H ₄ CHO) OC ₆ H40

121 (320) = OC ₆ H ₄ CHO (560) = OC ₆ H ₄

The intensity ratio of the formylproton (9.87 ppm) and the proton (8.55 ppm) between the trifluoromethyl and nitro groups in the NM-NMR spectrum also indicates the double-linked derivative.

The IR spectra show the CO band of the formyl group at 1700 cm ~ 'and the μ (ΖΗ band at 2740, 2820, 2860 cm @ -1).

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Example 5

5 - {[4- (Trifluoromethyl) -2,6-dinitro] phenoxy} -2-nitrobenzaldehyde (Compound No. 5)

6.05 g (0.017 mol) of 3 - {[4-trifluoromethyl) -2,6-dinitro] phenoxy] benzaldehyde (Preparation 1).

In Example 3), dissolved in a mixture of 12.5 mL of dichloromethane and 7.6 g of acetic anhydride, the solution was cooled to 10 ° C and slowly treated with nitric acid (1.8 mL, 0.027 mol) in 65% nitric acid and (8 mL, 98% sulfuric acid) was added dropwise.

Yield: 4.1 g, 60%.

129-130 ° C.

The color and form of yellow crystals, molecular formula: C ₄ H ₆ O ₈ F ₃ N _3, molecular weight: 401 (calculated).

Characteristics of the product mass spectrum are as follows:

m / e (r.i.) =

401 (180) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H (NO ₂ ) -CHO

382 (130) = F ₂ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H ₄ (NO ₂ ) CHO

235 (400) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂

166 (1000) = OC ₆ H ₃ (NO ₂ ) CHO

The 166 fragment clearly indicates that nitration has occurred.

Formylproton shifted from 9.85 ppm to 10.255 ppm.

The bands in the IR spectrum which are absorbed by the pCO at 1700 cm ^-1 and in the 1520-1550 cm ^-1 wavelength range are the μ as vibrations of the nitro groups. The μ s NO ₂ band appears at 1320, along with the extremely broad C-O-C band.

Example 6

5 - {[2- (Trifluoromethyl) -4,6-dinitro] phenoxy} -2-nitrobenzaldehyde (Compound No. 6)

8.4 g (0.024 mol) of 3 - {[2- (trifluoromethyl) -4,6-dinitro] phenoxy] benzaldehyde (Example 1, 4) were nitrated as described in Example 6.

Yield: 6.0 g, 64%.

112-122 ° C.

Color and shape of the product: yellow crystals, total formula: C ₁₄ H ₆ O ₈ N ₃ F ₃ , molecular weight 401 (calculated).

Typical fragments of the product mass spectrum are as follows:

m / e (r.i.) =

401 (140) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂ OC ₆ H ₃ (NO) -CHO

251 (220) = F ₃ C (NO ₂ ) ₂ O ₆ H ₂ O

235 (1000) = F ₃ C (NO ₂ ) ₂ C ₆ H ₂ 166 (500) = OC ₆ H ₃ (NO ₂ ) CHO

The Ή-NMR image is a brilliant example of readily recognizable or identifiable aro8 other protons. The large displacement of formylproton (10.25 ppm) is due to the adjacent nitro group. The proton between nitro groups (9.05 ppm) gives a nice meta linkage (J = 3Hz) with the proton between trifluoromethyl and nitro group (8.82 ppm).

The IR spectrum of pCO band appears at 1700 cm ^_1.

The autumn composition of the compositions of the present invention is given by weight (%).

Suspension concentrate (SC)

Example 7

No. 4 active ingredient 50.0% ethylene glycol 8.0% nonylphenyl polyglycol ether (10 EO) 5.0% polysaccharide 0.1% silicone oil 1.5% water 35.4%

Wet Powder (WP)

Example 8

No. 1 active ingredient 90.0% high dispersion silica 5.0% dispersant 5.0%

Granules (G)

Example 9

No. 6 active ingredient 5.0% limestone meal 69.0% ethylene glycol 3.0% highly dispersed silica 5.0% sodium lignin sulphate 3.0% water 13.5%

Dry flowable granules (WG)

Example 10

No. 2 active ingredient 80.0% sodium lauryl sulfate 2.0% sodium lignin sulfonate 7.0% water 3.0% kaolin 8.0%

Emulsion Concentrates (EC)

Example 11

No. 3 active ingredient 40.0% xylene 12.0% cyclohexanone 20.0% isophorone 20.0% polyoxyethylene sorbitan monooleate 5.0% nonylphenyl poly (glycol ether) (EO = 10) 3 0%

-8193194

Example 12

No. 1 active ingredient 20.0% xylene 60.0% isophorone 8.0% polyoxyethylene sorbitol trioleate 5.0% tributylphenyl poly (glycol ether) (EO = 10) 7.0% Nuclear foil

Example 13

a) 80 g of polyvinyl alcohol RHODOVIOL 4/125 P (viscosity of a 4% aqueous solution at 4 89 mole% hydrolyzed at 60 ° C) are added with stirring to 615 g of water at 60 ° C. After dissolution, 20 g of polyvinyl alcohol RHODOVIOL 30/20 m (viscosity of a 4% aqueous solution at 30 ° C at 30 ° C, 98 mol% hydrolyzed type) and 20 g of glycerol are added and stirred vigorously until homogenous. no solution is obtained. After standing for 24 hours, during which time the bubbles in the solution are removed, the solution is spread on a 0.50 mm thick glass plate with a watering knife and dried at room temperature. The film thus obtained is peeled off the glass sheet and has a thickness of 0.05 to 0.06 mm, and the film is easy to handle and tough (control film).

b) Using the same procedure as in a), prepare a solution for pouring the film in the same composition, to which 0.120 g of No. 6 is suspended in 5 ml of water. the active ingredient is mixed. After bubbling, a film is poured which, after drying, contains 1000 ppm of the active ingredient similar to that of Example a).

c) In a similar manner to that described in (b), 0.01220 g of No. 3 suspended in 5 ml of water are added to the water solution. the active ingredient is mixed. The resulting film contains 100 ppm of active ingredient.

d) Any of the active compounds of the present invention may be formulated in any manner with the active ingredient-containing film.

Biological examples

Example 14

Investigation of fungicidal efficacy

We prepare the agar plate in such a way that

Potato agar medium containing 2% dextrose was poured into 100 mm 0 Petri dishes and allowed to freeze.

The test compounds are prepared from% emulsion concentrates so that the stock solutions contain 20000, 4000, 800, 160, 32 ppm of active ingredient.

Suspensions of the fungal isolates included in the assays containing sufficient spores were prepared by diluting 1 drop of the water-dispersed spore suspension onto a microscope slide at 100-160 magnification based on an average of 5-10 fields per field of view.

1 ml of the prepared spore suspension is pipetted into 1 ml of each dilution series of the prepared test compound to obtain a solution containing 10,000, 2000, 400, 80, 16 ppm of lungicidal active substance + spore suspension and After standing for one minute, a sterile test tube was dipped in a mixture of lungicide-j-spore suspension and stripped on the prepared agar plate, followed by inoculation of the culture.

Once the fungi have developed well in the control treatments, we evaluate the growth of the fungus relative to the control according to the following rating scale

- no colony growth (0% relative to control) = poor colonial growth (10% relative to control) = medium colon growth (50% relative to control) = strong colonial growth (100% relative to control)

Intermediate values in%, e.g. 1.5 = 5%:

2.5 = 30%;

3.5 = 75% colon growth compared to 100% control.

In addition to the untreated control, the active compounds used in the process of the present invention are compared to 5 - {(2,6-dichloro-4- (trifluoromethyl)) phenoxy} -2-nitrobenzaldehyde having excellent lungicidal activity.

Tests show (Table 1) that the standard mold-like conidium fungi with 5% {{2,6-dichloro-4- (trifluoromethyl)] phenoxy} -2-nitrobenzaldehyde herbicide and fungicide 6 was effective. the active ingredient is greater than 3 to 4 to 5; s. The active ingredient strongly approaches, while the 1st and

No. 2 the efficacy of the active ingredient is slightly lower. This also means that in practical application, the so-called. For control of moldy conidium fungi it is advisable to use the standard amount of active ingredient, for example, for seed dressing 0.1 to 2.0 kg, preferably 0.2 to 1.0 kg active substance · t ^-1 seed, for plant treatment 0.1 to 10.0. preferably 0.5 to 3.0 kg of Xha- ¹ dose, 0.001 to 0.1% of the active ingredient in the preparation of the core film.

-9193194

Compound Colony Growth in Colonies Colony Growth Fungicidal Effect (active ingredient) Number of active substance repeats in average% by weight: in ppm (A) (B) (A) (B) (A) (B)

123 4 avg 1234 avg

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Fungicidal efficacy against Aspergillus niger (A) and Botrytis cinerea (B) co 'Φ

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-1 121

Example 15

Testing of herbicidal efficacy in a greenhouse

In order to demonstrate the fungicidal and non-herbicidal activity of the active compounds of the present invention, the following assays were performed.

30-30 seeds of Sinapis arvensis (wild rape) and Setaria glauca (loose muhar) were sown to 0.5 cm depth in water pots with 1.64 cm ² surface area and watered to water capacity. Preemergent treatments were applied immediately after sowing and postemergent treatments were sprayed with 10% emulsion-forming concentrate of the test compounds 10 days after emergence of the signaling plants, so that 0.1-0.33-1- 3 to 9 kg · ha ^-1 of active substance should be applied to the surface of the culture vessel. The degree of steady-state effect was expressed as a percentage, and the compounds were then determined to have a value of 0 ED ₅₀ (median effective dose) for the respective indicator plant.

The test results are shown in Table 2 5.

. spreadsheet

Active ingredient number: dose, kg ha ' ¹ Sinapis arvensis .Setaria glauca preemergent ED50 Busan.% postemergent ES50 pusz.Z preemer- postemergent ED50 pusz.Z gens Busan.% ED50 5 - {[2,6-dichloro-4- 0.1 0 18 0 0 - (triloromethyl) - 0.33 20 45 10 10 phenoxy-2-nitro- 1 73 0.6 80 0.35 90 0.5 72 0.2 benzaldehyde 3 98 96 100 100 9 100 100 100 100 0.1 0 0 0 0 0.73 0 0 0 0 First 1 Oh ⁰⁰ 0 00 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 Second 1 0 oo 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 Third 1 3 0 oo 0 0 9 10 0 0 oo 0 0 9 0 30 0 0 0.1 0 0 0 0 0.33 0 0 0 0 4th 1 0 ⁰⁰ 0 0 00 ⁰ 0 = 3 0 0 0 0 9 0 0 0 0 0.1 0 0 0 0 0.33 0 0 0 0 5th 1 0 0 o «o 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 6th 1 0 0 ^> 9 0 0-0 0> 9 3 0 10 0 20 9 0 30 0 30

PATENT CLAIMS

Claims (8)

PATENT CLAIMS CLAIMS 1. A fungicidal composition comprising as active ingredient from 0.001 to 95% by weight of a phenoxybenzaldehyde derivative (s) of the formula (I): R 1 and R ₃ are (trifluoromethyl) or nitro, with the meanings given above being 12 -12193194 TASS that R] and _R3 are not identical ' R ₂ is hydrogen or (3-formyl) phenoxy; X is hydrogen or chlorine, Y is a hydrogen atom or a nitro group, one or more solid and / or liquid carriers, preferably ground natural minerals, or an inert organic solvent, optionally with surfactant (s), preferably an anionic or nonionic emulsifier and / or dispersant. 2. A composition according to claim 1 wherein the active ingredient is 3 - {[5-chloro-4- (trifluoromethyl) -2-nitro]} phenoxybenzaldehyde. 3. A composition according to claim 1 wherein the active ingredient is 3 - {[4- (trifluoromethyl) -2,6-dinitro] phenoxy] benzaldehyde. Composition according to claim 4, characterized in that it contains 3 - {[2- (trifluoromethyl) -4,6-dinitro] phenoxy] benzaldehyde as active ingredient. 5. A composition according to claim 1, wherein the active ingredient is 2,4-fis-3-formylphenoxy-1- (trifluoromethyl) -3,5-dinitrobenzene. 6. A composition according to claim 1 wherein the active ingredient is 5 - {[4-trifluoromethyl) -2,6-dinitro] phenoxy} -2-nitrobenzaldehyde. 7. A composition according to claim 1 wherein the active ingredient is 5 - {[2- (trifluoromethyl) -4,6-dinitro] phenoxy} -2-nitrobenzaldehyde. 5 8. A method (I) of formula, new phenoxy benzaldehyde derivatives - wherein R, R _2, R _3, X and Y are Ϊ. The process of claim 1, with the proviso that when R 1 is nitro and R ₃ is trifluoromethyl then at least one of R ₂ , X and Y is other than hydrogen, characterized in that the inorganic solvent for 3-hydroxybenzaldehyde or its alkali metal salt, preferably its sodium or potassium salt, is preferably dipolar aprotic solvent - in the presence of a substituted benzene derivative of formula (II) - in which R 1, R ₂ , R 3, X and Y are And halogen, preferably chlorine, and the resulting phenoxybenzaldehyde derivative of formula (I) wherein R _{b is} R ₂ , R ₃ , X and Y is not defined above. recovering and optionally recrystallizing the reaction mixture from the reaction mixture, and then, if desired, the phenoxybenzaldehyde derivative of formula (Ia) wherein R _{b is} R ₂ , R _h R _2, R _3, X and Y are as defined wherein the fixed circle - 30 R _3, X and Y are as stated above - by nitration in a manner known in the general formula (I / b) phenoxy benzaldehyde derivative - 35.