DE2126149A1 - Halo-salicylanilide derivs - with acaricidal and fungicidal activity - Google Patents

Abstract

Title derivs of formula (I) (where X and Y are halogen, Z is H, acyl or alkoxycarbonyl (is not >6C), R1 is H, is not >4C alkyl, halogen, haloalkyl and/or NO2, R2 is H, halogen, alkyl and/or haloalkyl (is not >4C), Q is O or S, and m and n are 1,2 or 3), which are acaricides and broad-spectrum fungicides wall tolerated by plants, are prepd by reacting a salicyloyl halide of formula (II) with an aniline of formula (III) and opt. acylating the resulting (I; Z=H) with Z'-Cl(Z'=Z other than H).

Description

3,5-disubstituted salicylic acid-2'-phenoxy- and 2-phenylthioanilide, Process for their preparation and their fungicidal use The present invention relates to new 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides, which have acaricidal and fungicidal properties and processes for their preparation.

It has already become known that 3,5-disubstituted salicylic acid-4'-phenoxy- and 4'-phenylthioanilide can be used as anthelmintics (cf. Dutch Patent application 6,816,239). It is also known that 2-hydroxybenzoic acid anilide and the 4'-bromo derivative of which has fungicidal and bactericidal properties (cf. US patent 3,281,465).

It was also known that 3,5,6-trisubstituted 2-hydroxybenzoic acid anilides can be used as pesticides (see Dutch patent application 6 607 810; German Auslegeschriften 1 300 926, 1 542 944).

An acaricidal and fungicidal activity of salicylic acid phenoxy However, so far not known and phenylthioaniliden.

It has been found that the new 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides of the formula in which X and Y stand for halogen, Z stands for hydrogen, for acyl or alkoxycarbonyl with up to 6 carbon atoms, R1 for hydrogen, for alkyl with up to 4 carbon atoms, for halogen, for haloalkyl and / or nitro, R2 for hydrogen , stands for halogen, for alkyl and / or haloalkyl with up to 4 carbon atoms, Q stands for 0 or Sund m and n stands for an integer from 1 to 3, have very good acaricidal and fungicidal properties.

It has also been found that 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides of the formula (I) are obtained if a) 3,5-disubstituted salicylic acid chlorides of the formula in which X and Y have the meaning given above, with o-aminophenol ethers and thioethers of the formula in which Q, R1, R2, n and m have the meaning given above, or when b) 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides of the formula in which Q, R1, R2, X, Y, m and n have the meaning given above, with acid chlorides of the formula Z-Cl (V) in which Z has the meaning given above, in the presence of acid binders.

Surprisingly, show the 3,5-disubstituted according to the invention Salicylic acid-2'-phenoxy- and 2'-phenylthioanilide have a much higher acaricidal effect than 4 ', 5-dichloro-3 (4-chlorophenyl) salicilic acid anilide and a far higher fungicidal Effect as 2-hydroxybenzoic acid anilide, which is the chemically closest active ingredients are. The substances according to the invention thus represent an enrichment of technology.

If 3,5-dibromosalicylic acid chloride and 4,4'-dichloro-2-aminodiphenyl ether are used as starting materials, the course of the reaction can be represented by the following equation (method al): If 5,5'-dichloro-3-bromo-2-hydroxy-2'-phenylthio-benzoic anilide and ethyl chloroformate are used as starting materials, the course of the reaction can be represented by the following equation (method b) The 3,5-disubstituted salicylic acid chlorides and 3,5-disubstituted 2-hydroxy-2'-phenoxy (or 2'-phenylthio) -benzoic acid anilides to be used as starting materials are clearly defined by the formulas (II) and (IV). In these formulas, X and Y are preferably chlorine or bromine, R1 and R2 are preferably halogen, hydrogen or nitro; n and m are preferably integers from 1 to 3.

The o-amino-diphenyl ethers also to be used as starting materials and thioethers are clearly defined by the formula (III). In this formula R1 and R2 are preferably halogen, in particular chlorine, bromine or iodine, or they are preferably hydrogen or nitro; n and m are preferred for whole numbers from 1 to 3.

Acid chlorides of the formula (V) are also used as starting materials. In this formula, Z preferably represents acyl or alkoxycarbonyl with up to 4 Carbon atoms.

The compounds of the formulas (II), (III) and (V) are generally known.

The compounds of the formula (IV) are not yet known, but can be prepared by the processes mentioned under a).

As examples of the 3,5-disubstituted which can be used according to the invention Salicylic acid-2'-phenoxy- and 2'-phenylthioanilides of the formula (IV) are in detail named: 5,5'-dichloro-3-bromo-2'-p-chlorophenoxy-2-hydroxybenzoic anilide 3,5-dibromo-5'-chloro-2'-p-chlorophenoxy-2-hydroxybenzoic anilide 3-Bromo-5-chloro-2'-o-iodo-p-nitro-phenylthio-2-hydroxybenzoic acid anilide, 3-bromo-5,5'-dichloro-2s-phenylthio-2-hydroxybenzoic acid anilide 3,5-dichloro-2'-o-iodo-p-nitro-phenylthio-2-hydroxybenzoic anilide 3,5,5'-trichloro-2'-phenylthio-2-hydroxybenzoic anilide 3-Bromo-5,4 ', 5'-trichloro-2'-2 ", 4", 5 "-trichlorophenoxy-2-hydroxybenzoic anilide 3,5,4 ', 5'-Tetrachlor-2'-2 ", 4", 5 "-trichlorophenoxy-2-hydroxybenzoic anilide 3,5,5'-urichloro-2'-p-chlorophenoxy-Z-hydroxybenzoic anilide Suitable diluents in process a) according to the invention are all inert organic ones Solvent in question.

These preferably include higher-boiling organic hydrocarbons such as benzene, toluene, xylene or mesitylene or ethers such as dibutyl ether and dioxane.

All customary acid-binding agents can be used as acid-binding agents will. These preferably include alkali hydroxides, alkali carbonates and organic ones Bases. However, the reaction according to the invention can also be carried out without acid binders, if the hydrogen chloride formed is eliminated by boiling it off.

The reaction temperatures can vary over a wide range will. In general, between 50 ° and 150 ° C, preferably between 80 ° and 130 ° C.

When carrying out process a) according to the invention, one uses to 1 mole of the compound of the formula (I), 1 mole of the compound of the formula (II). Exceeding the stoichiometric ratios does not result in any significant improvement in the yield.

For isolation by process a), the solvent is except for one Quarter distilled off, the compounds of the formula (I) being obtained in crystalline form. They are cleaned by recrystallization Process b) the organic solvents mentioned under process a) in question; the acid binders mentioned under process a) are also used, in particular tertiary organic bases such as pyridine.

The reaction temperatures can also be within a relatively wide range can be varied. In general, the temperature is between 200 and 1000 ° C., preferably between 200 and 500C.

When carrying out process b) according to the invention, one uses to 1 mole of the compounds of the formula (IV) 1 to 1.1 moles of the compounds of the formula (V) or (VI). Another exceeding of the stoichiometric proportions does not bring any significant improvement in yield.

To isolate the compounds of the formula (I) by process b) is filtered off from the pyridine hydrochloride formed, the solvent stripped off in vacuo and the stretching stand is well dried. The purification of the compounds of formula (I) takes place by recrystallization.

Particularly effective substances which can be used according to the invention are im named individually: 5,5'-dichloro-3-bromo-2-acetoxy-2'-p-chlorophenoxy-benzoic anilide 3,5-dibromo-5r-chloro-2-hydroxy-2'-p-chlorophenoxy-benzoic anilide 3-erom-5,5'-dichloro-2-hydroxy-22-phenylthio-benzoic anilide 3-Bromo-5,5'-dichloro-2-acetoxy-2'-phenylthio-benzoic anilide 3,5,5'-trichloro-2-ethylcarbonyldioxy-2'-phenylthio-benzoic anilide 3,5,4 ', 5'-Tetrachloro-2-ethylcarbonyldioxy-2' - ", 4", 511-trichloro) -phenoxy-benzoic anilide The substances according to the invention are characterized by a very good acaricidal effect, against resistant mite strains.

The mites (Acari) include the spider mites (Tetranychidae) like the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), gall mites, e.g. the red currant mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); and finally ticks such as the beder tick (Ornithodorus moubata).

The active ingredients according to the invention also have a high degree of fungitoxicity Efficiency and a wide range of effects and have a relatively low Warm-blooded animal toxicity, which makes them easy to handle and undesirable for combating Fungal growth can be used in practice.

Their good tolerance to plants also allows them to be used against fungal plant diseases by treating the standing crop or individual parts of it or of the seeds or of the cultivated soil. The active ingredients are both effective against tracheomycosis-causing fungi that cause the plants attack from the ground, but also act against seed-borne fungi and against soil-dwelling mushrooms. The active compounds according to the invention can also be used are used against parasitic fungi on above-ground parts of plants. This is how they work against fungi of the genera Botrytis and Fusicladium.

The active ingredients can also be used to combat others with good results phytopathogenic fungi are used, e.g.

those fungi that cause diseases in rice and ornamental plants, in particular from Piricularia oryzae, Pellicularia sasakii, Cochliobolus miyabeanus, Cercospora musae, Phialosphora cinerescens.

Depending on their intended use, the new active ingredients can be converted into the usual ones Formulations such as solutions, emulsions, suspensions, powders, Pastes and granulates. These are prepared in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers, optionally using surface-active agents, i.e. emulsifying and / or Dispersants, e.g. in the case of using water as an extender organic solvents can optionally be used as auxiliary solvents can.

The main liquid solvents that can be used are: aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g.

Chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, Butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; as solid carrier materials: natural rock flour (e.g. kaolins, oner den, talc, chalk) and synthetic rock powder (e.g.

highly disperse silica, silicates); as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, z. B. alkylaryl polyglycol ethers, Alkyl sulfonates and aryl sulfonates; as dispersants e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients. The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %.

Die'Wirkstoffe can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsions, Suspensions, powders, pastes and granules can be used. The application happens in the usual way e.g. by spraying, atomizing, atomizing, scattering, dusting, Smoking, potting, gasifying, dry pickling, slurry pickling (slurry pickling), moist pickling, Wet pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas. In general, they are between 0.01 and 1%. The active ingredients can also be used with good success in the ultra-low-volume process (ULV) used where possible, formulations up to 95% or even to apply the 100% active ingredient alone.

Example A: Tetranychus test, resistant solvent: 3 parts by weight Dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether for production 1 part by weight of active ingredient is mixed with an appropriate active ingredient preparation the specified amount of solvent containing the specified amount of emulsifier, and dilute the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of about 10 - 30 cm, sprayed until dripping wet. These bean plants are strong with all stages of development of the common spider mite (Tetranychus urticae) infested.

After the times indicated, the effectiveness of the active ingredient preparation determined by counting the dead animals. The degree of destruction thus obtained becomes given in%. 100% means that all spider mites have been killed, 0 ffi means that no spider mites were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 1 below: Table 1 (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing centering degree in% in after 2 days ClvCO-NH-Cl OH (known) Cl Cl Cl to CO-NH to Cl 0.2 0 OH (known) Cl C1 t 0.2 95 0 Cl, CO-4 CO-NH 4 OCO-CH, Cl Example B: Pellicularia test / liquid active ingredient preparation Solvent: 1.9 parts by weight DMF dispersant: 0.1 part by weight alkylaryl polyglycol ether Water: 98 parts by weight water The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dispersant and dilutes the concentrate with the specified amount of water.

30 rice plants about 14 days old are sprayed with the spray liquid until dripping wet. The grass remains in a greenhouse until it is dry at temperatures of 22 ° to 240C and a relative humidity of approx 70%.

They are then mixed with a culture of Pellicularia grown on malt agar sasakii and inoculated in a room at 28-30 0C and 100 relative humidity set up.

5 days after the inoculation, the infestation is in all at the time of Inoculation leaves as a percentage of the untreated, but also inoculated leaves Control plants determined. 0% means no infestation, 100% means that the infestation is exactly as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in Table 2 below: Table 2 Pellicularia test / liquid active ingredient preparation Active ingredient infestation in ffi of the infestation of the untreated troll at an substance concentration in% of 4, p CO-NH 100 Ls / 0.05 i00 (known) in 0.05 25 Cl S > CO-WH < Cl Cl Example 1.

80 g (0.25 mol) 3,5-dibromosalicylic acid chloride and 65 g (0.25 mol) 4,4'-dichloro-2-aminodiphenyl ether are introduced into 800 ml of anhydrous xylene, slowly heated to reflux temperature and refluxed for 6 hours. Thereafter the solvent is concentrated to a quarter and the remaining solution put in a cool place. After cooling and suction, colorless crystals are obtained, which are recrystallized from petroleum ether. 128 g (98% of theory) are obtained 3,5-dibromo-5'-chloro-2-hydroxy-2'-p-chlorophenoxy-benzoic anilide of melting point 179-181 0C.

Example 2: 26.5 g (0.05 mol) of 3,5-dibromo-5,5'-dichloro-2-hydroxy-2'-pchlorophenoxy-benzoic anilide are dissolved in 350 ml of anhydrous benzene, 5 g (0.08 mol) of pyridine and 4.7 g (0.02 mol) of acetyl chloride, which was dissolved in 50 ml of anhydrous benzene, were added dropwise and the mixture was stirred at 35 ° C. for 16 hours, then the resulting pyridine hydrochloride was filtered off, the solvent was distilled off in vacuo and the oily residue , after drying in a high vacuum, recrystallized from a mixture of ligroin-benzene (1: 1). 23 g (81% of theory) of 3,5-dibromo-5,5'-dichloro-2-acetoxy-2'-p-chlorophenoxy-benzoic anilide with a melting point of 137-13800 are obtained.

Example 3: 81 g (0.3 mol) of 3-bromo-5-chloro-salicylic acid chloride and 70 g (0.3 mol) of 4-chloro-2-aminodiphenyl ether are slowly heated to reflux temperatures in 800 ml of anhydrous xylene and 6 Refluxed for hours. The solvent is then concentrated to a quarter and the remaining solution is kept cool. After cooling and suction, colorless crystals are obtained, which are recrystallized from petroleum ether. 118 g (73% of theory) of 3-bromo-5,5'-dichloro-2-hydroxy-2'-phenylthio-benzoic anilide with a melting point of 19200 are obtained.

Example 4: 31.8 g (0.075 mol) of 3,5,5'-trichloro-2-hydroxy-2'-phenylthiobenzoic acid anilide are dissolved in 350 ml of anhydrous benzene, 7.9 g of pyridine and then 10.8 g (0.1 mol) Ethyl chloroformate, which was dissolved in 50 ml of anhydrous benzene, was added dropwise and the mixture was stirred at 35 ° C. for 16 hours.

The resulting pyridine hydrochloride is then filtered off, the solvent is distilled off in vacuo and the oily residue after drying recrystallized from a mixture of ligroin-benzene (1: 1). 30 g of 3,5,5'-trichloro-2-ethyl-carbonyldioxy-2'-phenylthio-benzoic anilide are obtained of melting point 87-880C.

Tabel Example- XYZ R1 n R2 m Q melting number point ° C 5 Cl Cl H 2 "-I, 4". NO2 2 H 1 S 192 6 Cl Cl HH 1 5'-Cl 1 S 162-63 7 Cl Br H 2 ", 4", 5 "-Cl3 3 4 ', 5'-Cl 2 O 210-12 8 Cl Cl H 2 ", 4", 5 "-Cl3 3 4 ', 5'-Cl 2 O 214-15 9 Cl Cl H 4 "-Cl 1 5'-Cl 1 O 192-93 10 Cl Br H 2 "-I, 4" -NO2 2 H 1 S 188 11 Cl Br -COCH3 2 "-I, 4" -NO2 2 H 1 S 161 12 Cl Br -CO-OC2H5 2 "-I, 4" -NO2 2 H 1 S 168-70 Example- XYZ R1 n R2 m Q melting number point ° C 13 Cl Br -CO-CH3 H 1 5'-Cl 1 S 135-37 14 Cl Cl -CO-CH3 2 "-I, 4" -NO2 2 H 1 S 144-46 15 Cl Cl -CO-OC2H5 2 "-I, 4" -NO2 2 H 1 S 161-63 16 Cl Cl -CO-CH3 H 1 5'-Cl 1 S 125-27 17 Cl Br -Co-CH3 2 ", 4", 5 "-Cl3 3 3 ', 4'-Cl2 2 O 151-53 18 Cl Br -CO-OC2H5 2 ", 4", 5 "-Cl3 3 3 ', 4'-Cl2 2 O 163-64 19 Cl Cl -CO-CH3 2 ", 4", 5 "-Cl3 3 3 ', 4'-Cl2 2 O 159-60 20 Cl Cl -CO-OC2H5 2 ", 4", 5 "-Cl3 3 3 ', 4'-Cl2 2 O 163-65 21 Cl Cl -CO-CH3 4 "-Cl 1 5'-Cl 1 O 117-18 22 Br Br -CO-OCH3 4 "-Cl 1 5'-Cl 1 O 49-53 23 Br Br -CO-OC2H5 4 "-Cl 1 5'-Cl 1 O 138-40 Example melting number XYZ R¹ n R² m Q point ° C 24 Cl Cl -CO-OC2H5 4 "-Cl 1 5'-Cl 1 O 170-72 25 Cl Cl -CO-OC2H5 H 1 5'-Cl 1 S 87-88 26 Br Br -CO-CH3 4 "-Cl 1 5'-Cl 1 O 137-38

Claims (6)

Claims: 1. 3,5-disubstituted salicylic acid-2'-phenoxy and 2'-phenylthioanilide of the formula in which X and Y represent halogen, Z represents hydrogen, acyl or alkoxycarbonyl with up to 6 carbon atoms, R1 represents hydrogen, represents alkyl with up to 4 carbon atoms, represents halogen, represents haloalkyl and / or nitro, represents hydrogen, stands for halogen, for alkyl and / or haloalkyl with up to 4 carbon atoms, Q stands for 0 or S, m and n stand for an integer from 1 to 3. 2) Process for the preparation of 3,5-disubstituted salicylic acid-2'-phenoxy and 2'-phenylthioanilides, characterized in that 3,5-disubstituted salicylic acid chlorides of the formula in which X and Y have the meaning given above, with o-aminophenol ethers and thioethers of the formula in which Q, R1, R2, m and n have the meanings given above, or when 3, 5-disubstituted salicylic acid-2'-phenoxy and 2'-phenylthioanilides of the formula in which X, Y, Q, R¹, R², m and n have the meaning given above with acid chlorides of the formula Z-Cl (V) in which Z has the meaning given above, is reacted. 3) acaricidal and fungicidal agent, characterized by a content to 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilidep, according to Formula (I) in claim 7. 4) Methods of combating spider mites and phytopathogenic Mushrooms, characterized in that 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides according to formula (I) in claim 1 to spider mites and / or plant pathogenic fungi and / or their habitat can act. 5) Use of 3,5-disubstituted salicylic acid-2'-phenoxy and 2'-phenylthioanilides according to formula (I) in claim 1 for combating spider mites and / or phytopathogenic fungi. 6) Process for the production of an acaricidal and / or fungicidal Means, characterized in that one 3,5-disubstituted salicylic acid-2'-phenoxy- and 2'-phenylthioanilides according to formula (I) in claim 1 with extenders and / or surfactants mixed.