EP0705253A1

EP0705253A1 - Aralkylaminoquinazolines

Info

Publication number: EP0705253A1
Application number: EP94918866A
Authority: EP
Inventors: Roland Andree; Heinz-Wilhelm Dehne
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1993-06-24
Filing date: 1994-06-13
Publication date: 1996-04-10
Also published as: WO1995000496A1; AU7000494A; DE4321029A1; JPH08511786A

Abstract

New aralkylaminoquinazolines have formula (I), in which m equals 0, 1, 2, 3 or 4; n equals 1, 2, 3 or 4; R2 stands for hydrogen, halogen, cyano, nitro, carboxy, carbamoyl or possibly halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, dialkylaminocarbonyl or dialkylaminosulfonyl with up to 6 carbon atoms in the alkyl residues; R2 stands for hydrogen or alkyl with up to 6 carbon atoms; R3 stands for hydrogen, alkyl or possibly halogen-substituted alkylcarbonyl or alkylsulfonyl with up to 6 carbon atoms in the alkyl groups; R4 stands for hydrogen or possibly halogen-substituted alkyl with up to 6 carbon atoms; and R5 stands for halogen, cyano, nitro or possibly halogen-substituted alkyl with up to 6 carbon atoms. Also disclosed are their acid addition salts and metallic salt complexes, with the exception of the compounds S-(+)-7-chloro-N-(1-phenyl-ethyl)-4-quinazolinamine and R-(-)-7-chloro-N-(1-phenyl-ethyl)-4-quinazolinamine, a process for preparing the same and their use as fungicides.

Description

Aralkylaminoquinazolines

The invention relates to new aralkylaminoquinazolines, a process for their preparation and their use as fungicides.

It is already known that certain aralkylaminoquinazolines, e.g. S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazolinamine, fungicidal properties have (cf. EP-A 326328; cf. also EP-A 326329 and EP-A 326330).

However, the action of these compounds is not satisfactory in all respects.

There have now been new aralkylaminoquinazolines of the formula

in which m represents the numbers 0, 1, 2, 3 or 4,

n represents the numbers 1, 2, 3 or 4,

R ¹ for hydrogen, halogen, cyano, nitro, carboxy, carbamoyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, dialkylamino carbonyl or dialkylaminosulfonyl each having up to 6 carbon atoms in the alkyl radicals,

R ^{2 represents} hydrogen or alkyl having up to 6 carbon atoms,

R ^{3 represents} hydrogen, alkyl or in each case optionally substituted by halogen alkylcarbonyl or alkylsulfonyl, each with up to 6

Carbon atoms in the alkyl groups,

R ^{4 represents} hydrogen or alkyl optionally substituted by halogen with up to 6 carbon atoms, and

R ^{5 represents} halogen, cyano, nitro or alkyl optionally substituted by halogen with up to 6 carbon atoms,

as well as their acid addition salts and metal salt complexes,

with the exception of the compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazoline-amine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) - 4-quinazolinamine.

It has also been found that aralkylaminoquinazolines of the formula (I) and their acid addition salts and metal salt complexes are obtained when aralkylamines of the formula

in which

m, R ¹ , R ² and R ^{3 have} the meaning given above,

with haloquinazolines of the formula

in which

n, R .4. and. R have the meaning given above and

X represents halogen,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate subsequently adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Finally, it was found that the new aralkylaminoquinazolines of the formula (I) and their acid addition salts and metal salt complexes are notable for strong fungicidal activity.

Surprisingly, the aralkylaminoquinazolines of the formula (I) according to the invention have a considerably better fungicidal activity than the constitutionally most similar previously known active ingredients.

The aralkylaminoquinazolines according to the invention are generally defined by the formula (I).

m preferably represents the numbers 0, 1, 2 or 3.

n preferably represents the numbers 1, 2 or 3.

R preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, carboxy, carbamoyl or in each case optionally by fluorine and / or

Chlorine-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, Dialkylamino, dialkylaminocarbonyl or dialkylaminosulfonyl, each with up to 4 carbon atoms in the alkyl groups.

R ² preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.

R ³ preferably represents hydrogen, alkyl or alkylcarbonyl or alkylsulfonyl with 1 to 4 carbon atoms in the alkyl groups which are optionally substituted by fluorine and / or chlorine.

R ⁴ preferably represents hydrogen or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine and / or chlorine.

R ⁵ preferably represents fluorine, chlorine, bromine, iodine, cyano, nitro or, where appropriate, alkyl having 1 to 4 carbon atoms which is substituted by fluorine and / or chlorine.

The compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazolinamine and R - (-) - 7-chloro-N- (1-phenyl-ethyl) -4- quinazolinamine excluded.

m particularly preferably represents the numbers 0, 1 or 2.

n particularly preferably represents the numbers 1 or 2.

R ¹ particularly preferably represents hydrogen, fluorine, chlorine, bromine, cyano or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine , Methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl,

Ethylsulfinyl, methylsulfonyl or ethylsulfonyl, for dimethylamino, diethylamino, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminosulfonyl or diethylaminosulfonyl.

R ² particularly preferably represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl. R ³ particularly preferably represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, acetyl, propionyl, chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, methylsulfonyl, ethyl - sulfonyl or trifluoromethylsulfonyl.

R ⁴ particularly preferably represents hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by fluorine and / or chlorine.

R ⁵ particularly preferably represents fluorine, chlorine, bromine, cyano, nitro or methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine.

The compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) -4- quinazolinamine excluded.

A very particularly preferred group of compounds of the formula (I) are the chlorine-substituted aralkylaminoquinazolines of the formula

in which

m represents the numbers 0, 1 or 2,

R ^{1 represents} fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, R represents hydrogen, methyl, ethyl, n- or i-propyl,

R ^{3 represents} hydrogen, methyl or ethyl and

R ^{4 represents} hydrogen, methyl or ethyl,

as well as their acid addition salts and metal salt complexes.

Another very particularly preferred group of substances according to the invention are the compounds of the formula

in which

m represents the numbers 0, 1 or 2,

R ^{1 represents} fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl,

R ^{3 represents} hydrogen, methyl or ethyl and

R ^{4 represents} hydrogen, methyl or ethyl,

as well as their acid addition salts and metal salt complexes.

in which

m represents the numbers 0, 1 or 2,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl,

R ^{3 represents} hydrogen, methyl or ethyl and

R ^{4 represents} hydrogen, methyl or ethyl,

as well as their acid addition salts and metal salt complexes.

Preferred substances according to the invention are also addition products of acids and those aralkylaminoquinazolines of the formula (I) in which n, m, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given as preferred.

The acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, Fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids such as p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid, saccharin and thiosaccharin. In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. As well as IV. To VIII. Subgroup of the Periodic Table of the Elements and those aralkylaminoquinazolines of the formula (I) in which n, m, R ¹ , R ² , R ³ , R ⁴ and R have the meanings given as preferred.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred such acids in this connection are the hydrogen halide acids, e.g. hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

The compounds of the formula (I) according to the invention optionally contain an asymmetrically substituted carbon atom in the aralkyl radical and can then be present in various enantiomeric forms. The invention then relates both to the possible individual enantiomers and to the various possible - and therefore possibly also the racemic - mixtures of these enantiomers.

The general or residual definitions given above or in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediate products required in each case for the preparation.

These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds.

If, for example, 4,8-dichloro-quinazoline and 3-trifluoromethylbenzylamine are used as starting materials, the course of the reaction when carrying out the production process according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the aralkylamines to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I).

In formula (II), m, R, R and R preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for m, R ¹ , R ² and R ^{3 were} given.

The starting materials of the formula (II) are known and / or can be prepared by processes known per se (cf. DE-OS 2348801, DE-OS 2441651, DE-OS 2442845, DE-OS 2851039, EP-A 355351, EP-A 489682, Indian J. Chem. 13 (1975) 631).

Formula (III) provides a general definition of the haloquinazolines to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I).

In formula (III), n, R ⁴ and R ⁵ preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for n, R ⁴ and R ^{5 were} given. X preferably represents fluorine, chlorine or bromine, particularly preferably chlorine.

The starting materials of the formula (III) are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 68 (1946), 1299-1301, J. Chem. Soc. 1962, 561- 572, Z. Naturforsch. 37b (1982), 907-911).

The process according to the invention for the preparation of the new aralkylaminochinazolines of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl - And dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, esters such as methyl and ethyl acetate, nitriles such as, for example Acetonitrile and propionitrile, amides such as e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid triamide.

All acid binders which can normally be used for such reactions can be used as acid acceptors in the process according to the invention. Alkali metal hydroxides such as e.g. Sodium and potassium hydroxide, alkaline earth metal hydroxides such as e.g. Calcium hydroxide, alkali (hydrogen) carbonates and alcoholates such as sodium, potassium (hydrogen) carbonate, sodium and potassium tert-butoxide, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzyl amine, pyridine, l, 5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and l , 4-diazabicyclo [2,2,2] octane (DABCO).

The aralkylamines of the formula (II) used as starting materials can also serve as acid acceptors when used in a corresponding excess.

The reaction temperatures can be varied within a wide range in the process according to the invention. Generally one works at tempe- temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.

The ^; The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out the process according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent, if appropriate in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up in the process according to the invention is carried out in each case by customary methods (cf. the preparation examples).

The aralkylaminoquinazolines of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of formula (I) can be easily prepared by conventional salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid can be obtained and in a known manner, e.g. by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of formula (I), preference is given to those salts of metals which are already in the In connection with the description of the metal salt complexes according to the invention were mentioned as preferred metal salts.

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and addition to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides.

Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal diseases which come 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 leucotricha;

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 herpotricoids.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active compounds according to the invention are particularly suitable for the protective control of Plasmopara species on grapevines; they also show good effects e.g. against Erisyphe graminis, Septoria nodorum, Cochliobolus sativus and Pyrenophora teres.

To a certain extent, they also show activity against leaf insects and biting insects.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, and also in Formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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 wenches thylformamide and dimethyl sulfoxide, as well as water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellant, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

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

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

In the formulations, the active compounds according to the invention can be mixed with known fungicides, bactericides, acaricides, nematicides or

Insecticides are used to broaden the spectrum of activity or prevent development of resistance. In some cases synergism also occurs, which means that the effect of the mixture is greater than the sum of the effects of the individual components.

The mixing partners are e.g. the following substances in question:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4 ^, -trifluoromethoxy-4 ^, -trifluoromethyl-l, 3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxy quinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate, Calcium polysulfide, Captafol, Captan, Carbendazim, Carboxin, Quinomethionate (Quinomethionate), Chloroneb, Chloropicrin, Choloziloxilililililililililililililililililililililililililililililililililililililililililililililililililililonilonilonililililonilonilililililonilonilonililililililonilonililonilonililonililililonilolobolonilonililonilonilolilonilonobolilone silverone, chloronobloconolone, chloro-chloro-halo-zolonylolonoxolone Cyprofuram

Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, epimolazone, edifenazolone, edifenazolone, edifenazolone, edifenazolone, edifenazole

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, -Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futilanol, Futin , Furmecyclox, Guazatine,

Hexachlorobenzene, Hexaconazole, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (LBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and bordeaux Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,

Methasulf ocarb, methfuroxam, metiram, metsulfovax, myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb,

Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations, tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon,

Triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin,

Triticonazole,

Validamycin A, vinclozolin, zineb, ziram

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocentyl, Bethrin Bifin, Buthrin Carbob, Benfuracarbens Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 1 84699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocytezhrinhrinhrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofytoshrinhrinhrinhrin, Clofytoshrinhrinhrinhrin, Clofytoshrinhrinhrinhrinhrin, Clofytoshrinhrinhrinhrinhrinhrinhrinhrinhrin, Clofytoshrinhrinhrinhrinhrinhrin, , Cyhexatin, cypermethrin, cyromazine, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethifenin, Ethifenin, Ethifenin, Methamino, Emamofen, Emfom, Oxametheno Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothionx, Fhrionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufox, Fufox Heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, NI 25, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,

Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Primiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyrphithionof, Siliproxif, Sulfiproxyfif, Sulfiproxyfon, Pyriphronium, Quinphosphorus, Quinophosphorus , Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin7 Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Tri XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active substances as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, Spray powder, pastes, soluble powders, dusts and granules can be used. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to prepare the active ingredient or the active ingredient itself to inject the soil. The seeds of the plants can also be treated.

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.001% by weight, preferably between 0.5 and 0.001%.

In the seed treatment, amounts of active ingredient of 0.001 to -50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

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

The preparation and use of the active compounds according to the invention are illustrated by the following examples.

Preparation Examples:

example 1

A mixture of 2.0 g (10 mmol) of 4,8-dichloro-quinazoline, 3.1 g (20 mmol) of S1- (4-chlorophenyl) ethylamine and 50 ml of toluene is heated to boiling under reflux for 5 hours and then concentrated. The residue is stirred with concentrated sodium hydroxide solution and extracted with diethyl ether. The organic phase is concentrated and the residue is recrystallized from hexane.

2.7 g (85% of theory) of (S) -8-chloro-N- (1- (4-chlorophenyl) ethyl) -4-quinazolinamine with a melting point of 127 ° C. are obtained.

Analogously to Example 1 and in accordance with the general description of the process according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

E.g. m (position) RR ³ R n (position) melting

No. R ¹ (if necessary, isomerism)

CH, H

Table 1 - continued

Example, m (position) RR ³ R ⁴ n (position) melting

No. R ¹ (possibly Iso R ⁵ point

Starting materials of the formula (HD: Example (III- n

A mixture of 5.0 g (27.7 mmol) of 8-chloro-4-hydroxy-quinazoline, 8.1 g (38.8 mmol) of phosphorus (V) chloride and 50 ml of phosphoryl chloride is heated under reflux for 2 hours and then narrowed down. The residue is shaken with ice water / diethyl ether, the organic phase is washed with sodium hydrogen carbonate solution, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.

5.2 g (94% of theory) of 4,8-dichloro-quinazoline are obtained as a crystalline residue with a melting point of 182 ° C.

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

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in a moist chamber at 20 to 22 ° C. and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse at 21 ° C. and about 90% humidity for 5 days. The plants are then moistened and placed in a moist chamber for 1 day.

Evaluation is carried out 6 days after the inoculation.

Active substances, active substance concentrations and test results are shown in the following table:

Table A

Plasmopara test (vine) / protective

Table A - continued

Claims

Aralkylaminoquinazolines of the formula

in which m represents the numbers 0, 1, 2, 3 or 4,

n represents the numbers 1, 2, 3 or 4,

R ^{1 stands} for hydrogen, halogen, cyano, nitro, carboxy, carbamoyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, dialkylaminocarbonyl or dialkylaminosulfonyl each having up to 6 carbon atoms in the alkyl radicals, in each case substituted by halogen,

R represents hydrogen or alkyl having up to 6 carbon atoms,

R ^{3 represents} hydrogen, alkyl or alkylcarbonyl or alkylsulfonyl, each optionally substituted by halogen, each having up to 6 carbon atoms in the alkyl groups,

R represents hydrogen or optionally substituted by halogen

Alkyl having up to 6 carbon atoms, and

R represents halogen, cyano, nitro or alkyl optionally substituted by halogen with up to 6 carbon atoms, as well as their acid addition salts and metal salt complexes,

with the exception of the compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-chinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) - 4-quinazolinamine.

2. Aralkylaminoquinazolines of the formula (I) according to spoke 1, in which

m represents the numbers 0, 1, 2 or 3,

n represents the numbers 1, 2 or 3,

R ¹ for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, carboxy, carbamoyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, dialkylaminocarbonyl or dialkylaminosulfonyl, each optionally substituted by fluorine and / or chlorine, each with there are up to 4 carbon atoms in the alkyl groups,

R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms,

R ^{3 represents} hydrogen, alkyl or alkylcarbonyl or alkylsulfonyl with 1 to 4 carbon atoms in the alkyl groups which are optionally substituted by fluorine and / or chlorine,

R ^{4 represents} hydrogen or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine and / or chlorine and

R ^{5 represents} fluorine, chlorine, bromine, iodine, cyano, nitro or alkyl which has 1 to 4 carbon atoms and is optionally substituted by fluorine and / or chlorine,

with the exception of those of the compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-quinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) -4 -quinazolinamine. 3. Aralkylaminoquinazolines of the formula (I) according to spoke 1, in which

m represents the numbers 0, 1 or 2,

n represents the numbers 1 or 2,

R ¹ for hydrogen, fluorine, chlorine, bromine, cyano or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy which is optionally substituted by fluorine and / or chlorine , Ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, represents dimethylamino, diethylamino, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminosulfonyl or diethylaminosulfonyl

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl,

R ^{3 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, acetyl, propionyl, chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, methylsulfonyl, ethylsulfonyl or trifluoromethyl sulfon stands,

R ^{4 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine and

R ^{s represents} fluorine, chlorine, bromine, cyano, nitro or methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine,

with the exception of the compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-chinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) - 4-quinazolinamine. Aralkylaminoquinazolines of the formula

in which

m represents the numbers 0, 1 or 2,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl,

R> 3 represents hydrogen, methyl or ethyl and

R ^{4 represents} hydrogen, methyl or ethyl,

as well as their acid addition salts and metal salt complexes.

5. Aralkylaminoquinazolines of the formula

(lb) in which

m represents the numbers 0, 1 or 2,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl,

R ^{3 represents} hydrogen, methyl or ethyl and

R ^{4 represents} hydrogen, methyl or ethyl,

and their acid addition salts and metal salt compl.

6. Aralkylaminoquinazolines of the formula

in which

m represents the numbers 0, 1 or 2,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, R represents hydrogen, methyl or ethyl and

R represents hydrogen, methyl or ethyl,

as well as their acid addition salts and metal salt complexes.

7. Process for the preparation of aralkylaminoquinazolines of the formula

in which

m represents the numbers 0, 1, 2, 3 or 4,

n represents the numbers 1, 2, 3 or 4,

R ^{1 stands} for hydrogen, halogen, cyano, nitro, carboxy, carbamoyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, dialkylaminocarbonyl or dialkylaminosulfonyl each having up to 6 carbon atoms in the alkyl radicals, each optionally substituted by halogen,

R ^{2 represents} hydrogen or alkyl having up to 6 carbon atoms,

R ^{3 stands} for hydrogen, for alkyl or for alkylcarbonyl or alkylsulfonyl which are optionally substituted by halogen and each have up to 6 carbon atoms in the alkyl groups, R ^{4 represents} hydrogen or alkyl optionally substituted by halogen with up to 6 carbon atoms, and

as well as their acid addition salts and metal salt complexes,

with the exception of the compounds S - (+) - 7-chloro-N- (l-phenyl-ethyl) -4-chinazolinamine and R - (-) - 7-chloro-N- (l-phenyl-ethyl) - 4-quinazolinamine,

characterized in that aralkylamines of the formula

in which

m, R ¹ , R ² and R ^{3 have} the meaning given above,

with haloquinazolines of the formula

in which

n, R ⁴ and R have the meaning given above and

X represents halogen, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate subsequently adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

8. Fungicidal compositions, characterized by a content of at least one aralkylaminoquinazoline of the formula (I) according to claim 1 or of an acid addition salt or metal salt complex of an aralkylaminoquinoline of the formula (I).

9. Use of aralkylaminoquinazolines of the formula (I) according to Claim 1 or of their acid addition salts or metal salt complexes as fungicides.

10. A method for controlling unwanted fungi, characterized gekenn¬ characterized in that aralkylaminoquinazolines of formula (I) according to spoke 1 or their acid addition salts or metal salt complexes are allowed to act on fungi and / or their habitat.

11. A process for the preparation of fungicidal agents, characterized in that aralkylaminoquinazolines of the formula (I) according to spoke 1 or their acid addition salts or metal salt complexes are mixed with extenders and / or surface-active substances.