DE4208874A1 - Amino substd quinoline quinone utilisation - by fungicidal protection of plants and materials e.g. wood, leather and paint - Google Patents

Abstract

Use of amino-substd. quinoline-quinones of formula (I) (and their pure isomers and isomer mixts.) to combat fungi is new: n = 0 or 1; R1 = (a) H, halo, COOH, CN or NO2; (b) alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl or dialkylaminocarbonyl, all opt. substd. by one or more halo; (c) aryl, aryloxy, arylthio, arylsulphinyl or arylsulphonyl all opt. substd. by one or more halo, alkyl, haloalkyl, alkoxy and/or haloalkoxy; R2 = H, halo or alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl (all opt. substd. by one or more halo); or R1+R2 = a benzo gp.; Y = alkanediyl; Z = halo, alkoxy or alkylthio. USE/ADVANTAGE - (I) are useful in plant protection (e.g. against Phytophthora infestans, Venturia inaequalis or Fusarium culmorum) and, in addition to a fungicidal effect may also be useful against plant nematodes. Dosage is e.g. 0.001-50 (esp. 0.01-10)g/kg for treatment of seeds.

Description

The present invention relates to the use of partially known amino-substituted quinoline quinones as fungicides.

Various substituted quinoline quinones are known as po potential fungicides have become known, however, have up to ago as a means of combating fungi no practical loading interpretation obtained (cf. AT-PS 2 20 420 - cited in Chem. Abstracts 57: 3420 g; JP-A 5 80 67 672 - cited in Chem. Abstracts 99: 88069g).

Other substituted quinoline quinones are already available as Herbicides (cf. DE-OS 21 36 037) or as chemotherapy tika (see NL-PS 65 05 524 = US-PS 34 61 130) known or as endoparasiticides the subject of a previous, however not previously published patent application (cf. DE-A 41 20 477 of June 21, 1991). About fungicidal Eigen However, these connections have so far been nothing known.

It has now been found that amino-substituted quinoline quinones of the general formula (I)

in which
n stands for the numbers 0 or 1
R ¹ for hydrogen, halogen, carboxy, cyano, nitro, or for each optionally optionally to multiple times the same or different alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonyl, dialkylaminosulfonyl, alkoxy carbonyl or dialkylaminocarbonyl, or for each aryl, aryloxy, arylthio, arylsulfinyl or arylsulfonyl, optionally one to more times the same or different, substituted by halogen, alkyl, haloalkyl, alkoxy and / or haloalkoxy,
R ^{2 represents} hydrogen, halogen or, if appropriate, one to more times, the same or different halogen, substituted alkyl, alkoxy, alkyl thio, alkylsulfinyl or alkylsulfonyl, or together with R ^{1 forms} a benzo group,
Y stands for alkanediyl and
Z represents halogen, alkoxy or alkylthio
have strong fungicidal properties.

Aliphatic radicals such as alkyl, alone or in combination Settlements like alkoxy or alkylthio are straight-chain or branched, even if it is not specifically mentioned is.

Halogen stands for fluorine, chlorine, bromine or iodine, preferably for fluorine, chlorine or bromine, in compositions such as haloalkyl, haloalkoxy or haloalkylthio, preferably for fluorine and / or chlorine.

The general formula (I) stands for the possible iso mers of the formula (IA) and (IB) and for the mixtures of these isomers.

The invention preferably relates to the use of funicidal agents based on compounds of the formula (I) in which
n represents the numbers 0 or 1,
R ¹ for hydrogen, halogen, carboxy, cyano, nitro, or for each C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy, optionally substituted one to six times, identically or differently C ₄ - alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, C ₁ -C ₄ alkoxycarbonyl, dimethylaminocarbonyl or diethylaminocarbonyl, or, if appropriate, one to five times, identical or different halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ - C ₄ alkoxy and / or C ₁ -C ₄ haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl stands,
R ^{2 represents} hydrogen, halogen or, if appropriate, one to six times, the same or different, substituted by fluorine and chlorine, substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ - C ₄ alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl, or together with R ^{1 forms} a benzo group,
Y represents C ₁ -C ₄ alkanediyl and
Z represents halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio.

According to the invention, particular preference is given to using the compounds of the formula (I) in which
n represents the numbers 0 or 1,
R ¹ for hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, propyl, isopropyl, butyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, difluoromethoxy, trifluoromethoxy, trifluorethoxy, tetrafluoride orethoxy, Chlortrifluorethoxy, methylthio, ethyl thio, propylthio, isopropylthio, butylthio, Diflu ormethylthio, trifluoromethylthio, Chlordifluorme methylthio, nyl methylsulphinyl, trifluoromethylsulphinyl, methylsulphonyl, trifluoromethylsulphonyl, represents in each case optionally substituted by fluorine, chlorine, trifluoroacetic ormethyl or trifluoromethoxy-substituted Phe or phenoxy, Phenylthio or phenylsulfonyl,
R ^{2 represents} hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy,
Y for methylene (-CH₂-), ethylene (dimethylene, -CH₂CH₂-) propylene (trimethylene, - (CH₂) ₃-), ethylidene

or propylidene

stands and
Z represents chlorine, bromine, methoxy, ethoxy, propyloxy, methylthio, ethylthio or propylthio.

Examples of the Ver to be used according to the invention Compounds of formula (I) are in the following Table 1 listed.

Table 1

Examples of the compounds of the formula (I)

The compounds of formula (I) are known and / or can be made by methods known per se (see Collect. Czech. Chem. Commun 56 (1991), 1489- 1494; Indian J. Chem., Sect. B, 19B (1980), 512-513; DE-A 41 20 477 of June 21, 1991; Manufacturing examples).

The compounds of the formula (I)
(a) in the event that Z is halogen and n, R 1, R ² and Y have the meaning given above,
if haloquinoline quinones of the general formula (II)

in which
X represents halogen or methoxy and
Z ^{1 represents} halogen,
with amino compounds of the general formula (III)

in which
n, R ¹ , R ² and Y have the meaning given above,
optionally in the presence of a diluent, such as. B. ethanol, at temperatures between 20 ° C and 120 ° C, or
(b) when Z is alkoxy or alkylthio and n, R ¹ , R ² and Y have the meaning given above,
if compounds of the general formula (Ia) - obtainable as described under (a) -

in which
n, R ¹ , R ² and Y have the meaning given above and
Z ^{1 represents} halogen,
with alkanols or alkanethiols or their metal salts of the general formula (IV)

M-Z² (IV)

in which
M represents hydrogen, sodium or potassium and
Z ^{2 represents} alkoxy or alkylthio,
optionally in the presence of a diluent, such as. B. tetrahydrofuran, at temperatures between 0 ° C and 100 ° C.

The compounds of formula (I) in which Z is alkyl thio stands can also by implementing connections of formula (Ia) with alkali metal sulfides, such as. B. Well trium sulfide, and then with alkylating agents such as. B. Dimethyl or diethyl sulfate can be obtained (see Manufacturing examples).

The active ingredients according to the invention have a strong bio logical effect on and can be used to combat un desired pests can be used practically. The  Active ingredients are e.g. B. for use as plants suitable protective agents, especially as fungicides for loading fighting mushrooms.

Fungicides in crop protection are used for Control of Plasmodiophoromycetes, Oomycetes, Chytri diomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leuco tricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium),
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the necessary to combat plant diseases Kon centers allows treatment of above ground Parts of plants, of seedlings, and des Floor.  

The compounds of formula (I) show in particular strong protective action against Plasmopara species, such as e.g. B. Plasmopara viticola, which ver damages in viticulture causes, as well as against Venturia species, such as. B. Venturia inaequalis, which cause damage in fruit growing.

Against Pyricularia oryzae, Erysiphe graminis, Sep toria nodorum, Drechslera sorokiniana, Pyrenophora teres and Fusarium nivale a good effect is observed.

The compounds of formula (I) generally show a gu te in-vitro activity against harmful fungi. You can also use to combat harmful fungi in material protection be det.

Some of the compounds of formula (I) also show Effect against plant nematodes.

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, suspensions sions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric materials and in waste masses for seeds, as well as ULV formulations.

These formulations are produced in a known manner provides, e.g. B. by mixing the active ingredients with stretch agents, i.e. liquid solvents, under pressure standing liquefied gases and / or solid carriers substances, if necessary using upper surfactants, i.e. emulsifiers and / or  Dispersing agents and / or foaming agents. If water is used as an extender can e.g. B. also organic solvents as auxiliary sol be used. As a liquid solvent essentially come into question: aromatics, such as xylene, Toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorine benzenes, chloroethylene or methylene chloride, alipha table hydrocarbons, such as cyclohexane or paraf fine, e.g. B. petroleum fractions, alcohols such as butanol or Glycol and their ethers and esters, ketones, such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and Dimethyl sulfoxide, and water. With liquefied gas shaped extenders or carriers are such Liquids meant, which at normal temperature and are gaseous under normal pressure, e.g. B. Aerosol Propellants, such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide. As a solid support fabrics are possible: B. natural stone powder, such as kaolins, clays, talc, chalk, quartz, Atta pulgite, montmorillonite or diatomaceous earth and synthe table powder, such as finely divided silica, Alumina and silicates. As solid carriers for Granules are possible: B. broken and fractio nated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks. As an emulsifying and / or Foaming agents are possible: z. B. non-iono  gene and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolyzates. As a disperser middle come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxy can be used in the formulations methylcellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic Dyes such as alizarin, azo and metal phthalos cyanine dyes and trace nutrients, such as salts of Iron, manganese, boron, copper, cobalt, molybdenum and zinc be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in the form lations in a mixture with other known active ingredients are present, such as fungicides, insecticides, acaricides and Herbicides, as well as in mixtures with fertilizers and their growth regulators.  

The active ingredients as such, in the form of their formu lations or the application forms prepared from them, such as ready-to-use solutions, emulsifiable concentrates, Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules will. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering, ver dusting, foaming, brushing, etc. It is further possible, the active ingredients according to the ultra-low-volume ver drive or apply the drug preparation or inject the active ingredient into the soil yourself. It can also the seeds of the plants are treated.

In the treatment of parts of plants, the effects substance concentrations in the application forms in one larger range can be varied. They are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

When treating seeds, they are generally effective quantities of substances from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil are active ingredient concentrations from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02%, required at the site of action.  

The connections can also be used to protect technical Materials are used.

Technical materials are not alive according to the invention en Materials for use in technology have been prepared. For example, technical Materials created by active ingredients according to the invention who are protected against microbial change or destruction the should, adhesives, glue, paper and cardboard, texti lien, leather, wood, paints and plastic articles, Cooling lubricants and other materials that by Microorganisms can be attacked or decomposed. Tei are also part of the materials to be protected le of production plants, for example cooling water cycles, called by multiplication of microorga nisms can be affected. As part of the before lying invention as technical materials preferably adhesives, glues, papers and cartons, Le the, wood, paint, coolant and coolant called cycles.

As microorganisms that break down or change tion of the technical materials can be for example bacteria, fungi, yeast, algae and Called slime organisms. Preferably he act Active substances according to the invention against fungi, in particular Molds, wood-discoloring and wood-destroying fungi (Basidiomycetes).

Microorganisms of the following genera may be mentioned, for example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puteana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

Depending on the field of application, an inventive one Active ingredient in the usual formulations who converted such as solutions, emulsions, suspensions, powders, Pastes and granules.

These can be made in a manner known per se the, e.g. B. by mixing the active ingredients with a Extender that consists of liquid solvent and / or solid carrier material exists, optionally under Ver use of surface-active agents, such as emulsifiers and / or dispersants, where appropriate in Organi if water is used as an extender Use solvents such as alcohols as aids can be detected.

Liquid solvents for the active ingredients can for example water, alcohols, such as lower aliphatic  Alcohols, preferably ethanol or isopropanol, or Benzyl alcohol, ketones, such as acetone or methyl ethyl ketone, liquid hydrocarbons, such as gasoline fractions, halo hydrogenated hydrocarbons such as 1,2-dichloroethane.

Microbicidal agents generally contain the active ingredients NEN in an amount of 1 to 95%, preferably from 10 to 75%.

The application concentrations of the invention Active ingredients depend on the type and occurrence the microorganisms to be combated, as well as after the composition of the material to be protected. The optimal one The amount used can be determined by test series. in the the application concentrations are generally in the range range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The active compounds according to the invention can also be mixed with other known active ingredients. Example The following active ingredients may be mentioned wisely: benzylal alcohol mono (poly) hemiformal and other formaldehyde compounds, benzimidazolyl methyl carbamates, Tetramethylthiuram disulfide, zinc salts of dialkyldithio carbamates, 2,4,5,6-tetrachloroisophthalonitrile, thia zolylbenzimidazole, mercaptobenzthiazole, 2-rhodanido methylthiobenzthiazole, organotin compounds, methyl lenisthiocyanate, N-alkyl and N-aryl iodopropargyl carba mate, triazole and imidazole fungicides, phenol derivatives, such as 2-phenylphenol, (2,2'-dihydroxy-5,5-dichloro) -di phenylmethane, 3-methyl-4-chlorophenol and 3-methyl-4- chlorophenol.

Examples of use: Example A

Plasmopara test (vines) / protective
Solvent: 4.7 parts by weight of acetone.
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable active ingredient preparation mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on, the Plants with an aqueous spore suspension from Plasmo para viticola and then remain in for 1 day a moist chamber at 20 to 22 ° C and 100% relative Humidity. Then the plants 5 Days in a greenhouse at 22 ° C and approx. 80% humidity set up. The plants are then moistened and placed in a wet room for 1 day.

Evaluation is carried out 6 days after the inoculation.

This test shows a strong fungicidal activity e.g. B. the compounds according to the following preparation games: (1), (9), (10), (11,), (13) and (60).  

Table A

Plasmopara test (vine) / protective

Example B

Venturia test (apple) / protective
Solvent: 4.7 parts by weight of acetone.
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable active ingredient preparation mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on, the Plants with an aqueous conidia suspension of Apple scab pathogen (Venturia inaequalis) inoculated and then remain at 20 ° C and 100% relative for 1 day Humidity in an incubation cabin.

The plants are then in the greenhouse at 20 ° C and a relative humidity of approx. 70% poses.

Evaluation is carried out 12 days after the inoculation.

This test shows a strong fungicidal activity e.g. B. the compounds according to the following preparation games: (1), (6), (10), (11), (13), (15), (22), (57) and (60).  

Table B

Venturia test (apple) / protective

Manufacturing examples example 1

5.0 g (21.9 mmol) of 6,7-dichloro-quinoline-5,8-quinone submitted in 35 ml of absolute ethanol and with 10.6 g (65.7 mmol) 4-trifluoromethyl-aniline added. Then it will be until complete conversion (2.5 hours) at reflux temperature stirred and then cooled to 0 ° C. The precipitated solid is filtered off and dried net.

7.7 g of crude product of a regioisomer mixture are obtained that over a silica gel column (silica gel 60 - Merck, grain size: 0.040-0.063 mm) with the superplasticizer Toluene: ethanol (15: 1) is chromatographed.  

6-chloro-7- (4-trifluoromethyl-phenylamino) -quinoline-5,8- quinone Mp .: 238-239 ° C 1.5 g (19.5% of theory)

¹ H NMR (CDCl ₃ , δ): 7, 16; 7.63 (2d, 4H, aromatic; J = 8.4 Hz); 7.73 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz; JH ^B , H ^C : 7.9 Hz); 7.85 (s, 1H, NH); 8.53 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 9.01 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz) ppm

7-chloro-6- (4-trifluoromethyl-phenylamino) -quinoline-5,8- Quinone (= Example No. 1 in Table 1) Mp .: 188-190 ° C 2.3 g (29.9% of theory)

¹ H NMR (DMSO-d ₆ , δ): 7.28; 7.65 (2d, 4H, aromatic; J = 8.4 Hz) 7.83 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz; JH ^B , H ^C : 7.9 Hz ); 8.39 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 9.00 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz); 9.57 (s, 1H, NH) ppm

Example 2 (= Example No. 11 in Table 1)

5.0 g (0.022 mol) of 7-chloro-6-methoxy-quinoline-5,8-quinone are placed in 150 ml of hot ethanol and 8.6 g (0.044 mol) of 4-trifluoromethylthio-aniline was added dropwise. Then will return until complete sales (24 hours) flow temperature stirred and the entire batch to 0 ° C. cooled down. The precipitated crystals are suctioned off, Washed with a little cold ethanol and made from ethanol recrystallized.

6.7 g (77.9% of theory) of 7-chloro-6- (4-tri fluoromethylthio-phenylamino) -quinoline-5,8-quinone.

Mp: 192-193 ° C

¹ H NMR (DMSO-d ₆ , δ): 7.24; 7.64 (2d, 4H, aromatic; J = 8.5 Hz); 7.82 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz, JH ^B , H ^C : 7.9 Hz); 8.40 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 9.01 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz); 9.56 (s, 1H, NH) ppm

Example 3

4.6 g (10.9 mmol) of 6- [3,5-bis (trifluoromethyl) phenylami no] -7-chloro-quinoline-5,8-quinone in 40 ml of ethanol presented and at room temperature with 2.6 g (10.9 mmol) Sodium sulfide nonahydrate (dissolved in 40 ml water) ver puts. The previously red solution turns blue black. The mixture is stirred for 5 minutes at room temperature, dripped in 1.0 g (10.9 mmol) of dimethyl sulfate and he refluxed for another 15 minutes. After one hour Stirring at room temperature, the entire batch in Va concentrated in vacuo, the residue stirred with water and the separated solid recrystallized from ethanol.

1.0 g (21.2% of theory) of 6- [3,5-bis (triflu ormethyl) phenylamino] -7-methylthio-quinoline-5,8-quinone.

Mp: 135-137 ° C

¹ H NMR (CDCl ₃ , δ): 2.28 (s, 3H, -SCH ₃ ); 7.39 (s, 2H, aroma); 7.63 (s, 1H, aroma); 7.66 (dd, 1H, H ^B ; JH ^A , JH ^B : 4.8 Hz; JH ^B , H ^C : 7.9 Hz); 7.85 (s, 1H, NH); 8.43 (dd, 1H, H ^C , JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 9.03 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz) ppm

Example 4

10 g (28.3 mmol) of the mixture of 6-chloro-7- (4-triflu ormethyl-phenylamino) - and 7-chloro-6- (4-trifluoromethyl phenylamino) -quinoline-5,8-quinone in 100 ml abso lutem tetrahydrofuran and portioned with 3.4 g (34.6 mmol) of sodium 1-propanethiolate were added. The Mix until complete conversion (15 to 20 Hours) at room temperature. Then the ge the entire reaction mixture is concentrated in vacuo, the syrupy one Residue taken up in 200 ml of chloroform, with 200 ml 0.5 N hydrochloric acid shaken out and washed with water. The organic phase is dried over sodium sulfate and then distilled off the solvent. The remaining crude product of the regioisomer mixture can over a silica gel column (Kieselgel 60-Merck, grain size: 0.040-0.063 mm) with the eluent toluene: Etha nol (10: 1) are chromatographed.  

6- (1-Propylthio) -7- (4-trifluoromethyl-phenylamino) -chino lin-5,8-quinone Mp .: 175-176 ° C 1.8 g (16.2% of theory)

¹ H NMR (DMSO-d ₆ , δ): 0.73 (t, 3H, -CH ₃ ; J = 7.3 Hz); 1.31 (m, 2H, -CH ₂ -; J = 7.3 Hz); 2.56 (t, 2H, -SCH ₂ -; J = 7.3 Hz); 7.20; 7.62 (d, 4H; aromatic J = 8.4 Hz); 7.82 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz; JH ^B , H ^C : 7.9 Hz); 8.36 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 8.96 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz); 9.49 (s, 1H, NH) ppm.

7- (1-Propylthio) -6- (4-trifluoromethyl-phenylamino) -chino lin-5,8-quinone Mp .: 85-86 ° C 1.65 g (14.7% of theory)

¹ H NMR (DMSO-d ₆ , δ): 0.74 (t, 3H, -CH ₃ ; J = 7.3 Hz); 1.32 (m, 2H, -CH ₂ -; J = 7.3 Hz); 2.57 (t, 2H, -SCH ₂ -; J = 7.3 Hz); 7.19; 7.61 (2d, 4H; aromatic J = 8.4 Hz); 7.79 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz; JH ^B , H ^C : 7.9 Hz); 8.38 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz; JH ^C , H ^A : 1.7 Hz); 8.98 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz); 9.39 (s, 1H, NH) ppm.

Analogous to Examples 1 to 4, the wide ones can also be used ren compounds of the formula listed in Table 1 (I) can be produced.  

Examples of the production of the starting products Example (II-1) 7-chloro-6-methoxy-quinoline-5,8-quinone

To a suspension of 6.6 cooled to 0 to -5 ° C g (0.029 mol) of 6,7-dichloro-quinoline-5,8-quinone in 200 ml Methanol is added in portions to 2.0 g (0.029 mol) of potassium given methanolate. A slight warmth escapes winding up. Then there is another 2 hours at room temperature stirred and the entire batch in a vacuum constricted. The remaining residue is washed with water washed and recrystallized from a little methanol.

4.5 g (69.4% of theory) of 7-chloro-6-methoxy are obtained quinoline-5,8-quinone.

Mp .: 175-177 ° C

¹ H NMR (DMSO-d ₆ , δ): 4.24 (s, 3H, -OCH ₃ ); 7.85 (dd, 1H, H ^B ; JH ^B , H ^A : 4.8 Hz; JH ^B , H ^C : 7.9 Hz); 8.38 (dd, 1H, H ^C ; JH ^C , H ^B : 7.9 Hz, JH ^C , H ^A : 1.7 Hz); 9.00 (dd, 1H, H ^A ; JH ^A , H ^C : 1.7 Hz; JH ^A , H ^B : 4.8 Hz) ppm.

Claims (7)

1. Use of amino-substituted quinoline quinones of the general formula (I) in which
n represents the numbers 0 or 1,
R ¹ for hydrogen, halogen, carboxy, cyano, nitro, or for each optionally optionally mono- to polysubstituted, identically or differently, halogen, substituted alkyl, alkoxy, alkyl thio, alkylsulfinyl, alkylsulfonyl, dialkyl aminosulfonyl, alkoxycarbonyl or dialkyl aminocarbonyl, or for each optionally aryl, aryloxy, arylthio, arylsulfinyl or arylsulphonyl which is mono- to polysubstituted, identically or differently, by halogen, alkyl, haloalkyl, alkoxy and / or haloalkoxy,
R ^{2 represents} hydrogen, halogen or, where appropriate, one to more times, identically or differently, substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, or together with R ^{1 forms} a benzo group,
Y stands for alkanediyl and
Z represents halogen, alkoxy or alkylthio, and their pure isomers and isomer mixtures for combating fungi. 2. Use of compounds of formula (I) according to claim 1, in which
n represents the numbers 0 or 1,
R ¹ for hydrogen, halogen, carboxy, cyano, nitro, or for C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ substituted by fluorine and chlorine in each case optionally one to six times, identically or differently _4- alkylthio, C ₁ -C ₄ -alkyl sulfinyl, C ₁ -C ₄ -alkylsulfonyl, dimethyl aminosulfonyl, diethylaminosulfonyl, C ₁ -C ₄ -alkoxycarbonyl, dimethylaminocarbonyl or diethylaminocarbonyl, or, if appropriate, one to five times, identical or different halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and / or C ₁ -C ₄ haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl ,
R ² for hydrogen, halogen or in each case optionally one to six times, identically or differently substituted by fluorine and chlorine, substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl,
or forms a benzo group together with R ¹ ,
Y represents C ₁ -C ₄ alkanediyl and
Z represents halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio, and their pure isomers and isomeric mixtures for combating fungi. 3. Use of compounds according to claim 1, wherein in the formula (I)
n represents the numbers 0 or 1,
R ¹ for hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, propyl, isopropyl, butyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, difluoromethoxy, trifluoromethoxy, trifluoroethoxy, tetrafluoroethoxy , Chlorotrifluoroethoxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, or, if appropriate, by trifluoromethyl, chloromethyl, phenylluoromethyl, chloromethyl, phenifluoromethyl, chloromethyl, phenyl, phenyl, phenyl, phenyl, or fluorinated, phenifluoromethyl, phenyl, phenyl, or fluorine, phenyl, methoxy, chloromethyl, or phenylsulfonyl,
R ^{2 represents} hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy,
for methylene (-CH ₂ -), ethylene (dimethylene, -CH ₂ CH ₂ -) propylene (trimethylene, - (CH₂) ₃-), ethylidene or propylidene stands and
Z stands for chlorine, bromine, methoxy, ethoxy, propyloxy, methylthio, ethylthio or propylthio and mix their pure isomers and isomers to fight fungi. 4. Fungicidal agent, characterized by a Content of at least one amino substituted Quinolinequinone of formula (I) according to claim 1. 5. Process for combating fungi, thereby characterized in that at least one amino substance tuated quinolinequinone of formula (I) according to An say 1 to mushrooms and / or their habitat lets work. 6. Process for the preparation of fungicidal compositions, characterized in that one is amino-substituted Quinoline quinones of formula (I) according to claim 1 with Extenders and / or surfactants mixed. 7. Mushrooms according to claim 1 are fungi in plants protection and material protection.