DE102008000872A1 - New pyrazine compounds useful in the fungicidal agent, for combating plant pathogenic fungus in protecting materials, plants, ground or seeds and to treat cancer - Google Patents

Abstract

Pyrazine compounds (I) and their salts are new. Pyrazine compounds of formula (I) and their salts are new. R1>, R4>halo (preferred), CN, 1-8C alkoxy or phenyl-1-4C alkyl; R2>1-12C alkyl, 1-10C haloalkyl, 2-10C alkenyl, 2-10C haloalkenyl, 2-10C alkynyl, 2-10C haloalkynyl, 3-6C cycloalkyl, 3-8C cycloalkenyl, 3-12C cycloalkenyl, 3-6C halocycloalkyl, 3-12C halocycloalkenyl, aryl (preferred) or aromatic heterocycle (containing 1-4 R1a group and other than carbon atoms, up to 4 N or 0-2 N, S or O as a ring atoms, where the aromatic groups are 5-10 membered ring system); R1a : CN, nitro, OH, carboxyl, 1-6C alkyl, 2-6C alkynyl, 3-6C cycloalkyl, 3-8C cycloalkenyl, 1-6C alkoxy, 2-6C alkenyloxy, 3-6C alkynyloxy, 3-6C cycloalkoxy, 3-6C cycloalkenyloxy, C(O)R1n, C(O)OR1n, C(S)OR1n, C(O)SR1n, C(S)SR, OC(O)OR1n, 1-6C alkylthio, amino, 1-6C alkylamino, di-1-6C alkylamino, 1-6C alkylene, oxy-1-4C alkylene, oxy-1-3C alkylenoxy, where the divalent groups are bonded to the same atom or at the adjacent atoms, phenyl, naphthyl, 5-10 membered saturated, partially unsaturated or aromatic heterocycle (containing other than the carbon atoms, an up to 4 N or up to 3 N, S or O as a ring atom); R1n : 1-8C alkyl, 3-8C alkenyl, 3-8C alkynyl, 3-6C cycloalkyl or 3-6C cycloalkenyl, where the aliphatic, alicyclic or aromatic groups in R1a and R1n are halogenated partially or completely and carries 1-3 groups of R1b; R1b : halo, CN, nitro, OH, mercapto, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyl, aminothiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl group contains 1-6 carbon atom and the alkenyl- or alkynyl group contains 2-8 carbon atoms, cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, where the cyclic system contains 3-10 ring member, aryl, aryloxy, arylthio, aryl-1-6C alkoxy, aryl-1-6C alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl residue is preferably 6-10 ring members containing 5-6 membered hetaryl residues, where the cyclic systems are partially or completely halogenated and/or substituted by alkyl- or haloalkyl group; R3>aryl (preferred) or heteroaryl, containing other than carbon atom, up to 4 N or 0-2 N, S or as a ring atom, where the group is 5-10 membered ring system, containing a group L1> in ortho position to the bonding to the pyridazine-basic unit and at least a further group Lm; L1>halo, 1-4C alkyl, 1-4C haloalkyl; L : halo, OH, OCN, CN, nitro, 1-8C alkyl, 1-8C haloalkyl, 2-10C alkenyl, 2-10C haloalkenyl, 2-10C alkynyl, 3-6C cycloalkyl, 3-6C halocycloalkyl, 3-6C cycloalkenyl, 1-8C alkoxy, 1-8C haloalkoxy, 2-10C alkenyloxy, 2-10C alkynyloxy, 3-6C cycloalkyloxy, 3-6C cycloalkenyloxy, amino, 1-4C alkylamino, di-(1-4C)-alkylamino, C(O)-R1z, C(S)-R1z, S(O)n-R1z, 1-8C alkoxyimino- (1-8C)-alkyl, 2-10C alkenyloxyimino-(1-8C)-alkyl, 2-10C alkynyloxyimino-(1-8C)-alkyl, 2-10C alkynylcarbonyl, 3-6C cycloalkylcarbonyl, or 5-10 membered saturated, partially unsaturated or aromatic heterocyclic containing 1-4 heteroatoms of O, N or S; R1z : H, 1-4C alkyl, 1-2C haloalkyl, 1-4C alkoxy, 2-4C alkenyloxy, 2-4C alkynyloxy, where the group R1z is substituted with 1-3 R1b group; n : 0-2; and m : 1-4. Independent claims are included for: (1) the preparation of (I); (2) 1,2-dihydro-pyridazine-3,6-dione compound of formula (II); a fungicidal agent containing a solid or liquid carrier and (I); and (3) a seed containing (I) in a quantity of 1-1000 g/100 kg. [Image] [Image] ACTIVITY : Fungicide; Cytostatic. MECHANISM OF ACTION : None given.

Description

in der die Substituenten folgende Bedeutung haben:
R¹, R⁴ unabhängig voneinander Halogen, Cyano oder C₁-C₈-Alkoxy;
R² C₁-C₁₂-Alkyl, C₁-C₁₀-Halogenalkyl, C₂-C₁₀-Alkenyl, C₂-C₁₀-Halogenalkenyl, C₂-C₁₀-Alkinyl, C₂-C₁₀-Halogenalkinyl, C₃-C₆-Cycloalkyl, C₃-C₈-Cycloalkenyl, C₃-C₁₂-Cycloalkenyl, C₃-C₆-Halogencycloalkyl, C₃-C₁₂-Halogencycloalkenyl, Aryl oder aromatischer Heterocyclus, enthaltend neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringlieder, wobei die aromatischen Gruppen fünf-, sechs-, sieben-, acht-, neun- oder zehngliedrige Ringsysteme darstellen; und R² eine, zwei, drei oder vier gleiche oder verschiedene Gruppen R^a enthalten kann, die unabhängig voneinander ausgewählt sind aus:
R^a Cyano, Nitro, Hydroxy, Carboxyl, C₁-C₆-Alkyl, C₂-C₆-Alkinyl, C₃-C₆-Cycloalkyl, C₃-C₈-Cycloalkenyl, C₁-C₆-Alkoxy, C₂-C₆-Alkenyloxy, C₃-C₆-Alkinyloxy, C₃-C₆-Cycloalkoxy, C₃-C₆-Cycloalkenyloxy, c(O)R^Π, C(o)OR^Π, C(S)OR^Π, C(O)SR^Π, C(S)SR^Π, OC(O)OR^Π, C₁-C₆-Alkylthio, Amino, C₁-C₆-Alkylamino, Di-C₁-C₆-alkylamino, C₁-C₆-Alkylen, Oxy-C₁-C₈-alkylen, Oxy-C₁-C₃-alkylenoxy, wobei divalente Gruppen an das selbe Atom oder an benachbarte Atome gebunden sein können, Phenyl, Naphthyl, fünf-, sechs-, sieben-, acht-, neun- oder zehngliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringlieder;
R^Π C₁-C₈-Alkyl, C₃-C₈-Alkenyl, C₃-C₈-Alkinyl, C₃-C₆-Cycloalkyl oder C₃-C₆-Cycloalkenyl;
wobei die aliphatischen, alicyclischen oder aromatischen Gruppen in den vorgenannten Gruppen R^a und R^Π ihrerseits partiell oder vollständig halogeniert sein und/oder eine, zwei oder drei Gruppen R^b tragen können:
R^b Halogen, Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Alkyl, Halogenalkyl, Alkenyl, Alkoxy, Halogenalkoxy, Alkenyloxy, Alkinyloxy, Alkylthio, Alkylamino, Dialkylamino, Formyl, Alkylcarbonyl, Alkylsulfonyl, Alkylsulfoxyl, Alkoxycarbonyl, Alkylcarbonyloxy, Alkoxycarbonyloxy, Aminocarbonyl, Aminothiocarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkylaminothiocarbonyl, Dialkylaminothiocarbonyl, wobei die Alkylgruppen in diesen Gruppen 1 bis 6 Kohlenstoffatome enthalten und die genannten Alkenyl- oder Alkinylgruppen in diesen Gruppen 2 bis 8 Kohlenstoffatome enthalten; Cycloalkyl, Cycloalkoxy, Heterocyclyl, Heterocyclyloxy, wobei die cyclischen Systeme 3 bis 10 Ringglieder enthalten; Aryl, Aryloxy, Arylthio, Aryl-C₁-C₆-alkoxy, Aryl-C₁-C₆-alkyl, Hetaryl, Hetaryloxy, Hetarylthio, wobei die Arylreste vorzugsweise 6 bis 10 Ringglieder, die Hetarylreste 5 oder 6 Ringglieder enthalten, wobei die cyclischen Systeme partiell oder vollständig halogeniert und/oder durch Alkyl- oder Halogenalkylgruppen substituiert sein können;
R³ Aryl oder Heteroaryl, enthaltend neben Kohlenstoffatomen ein bis vier Stickstoffatome oder null bis zwei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringlieder, wobei die Gruppen fünf-, sechs-, sieben-, acht-, neun- oder zehngliedrige Ringsysteme darstellen, welche neben einer Gruppe L¹ in ortho-Position zu der Bindung an das Pyridazin-Grundgerüst, mindestens eine weitere Gruppe
L_m tragen können:
L¹ Halogen, C₁-C₄-Alkyl, C₁-C₄-Halogenalkyl;
L Halogen, Hydroxy, Cyanato (OCN), Cyano, Nitro, C₁-C₈-Alkyl, C₁-C₈-Halogenalkyl, C₂-C₁₀-Alkenyl, C₂-C₁₀-Halogenalkenyl, C₂-C₁₀-Alkinyl, C₃-C₆-Cycloalkyl, C₃-C₆-Halogencycloalkyl, C₃-C₆-Cycloalkenyl, C₁-C₈-Alkoxy, C₁-C₈-Halogenalkoxy, C₂-C₁₀-Alkenyloxy, C₂-C₁₀-Alkinyloxy, C₃-C₆-Cycloalkyloxy, C₃-C₆-Cycloalkenyloxy, Amino, C₁-C₄-Alkylamino, Di-(C₁-C₄)-Alkylamino, C(O)-R^Φ, C(S)-R^Φ, S(O)_n-R^Φ; C₁-C₈-Alkoxyimino-(C₁-C₈)-alkyl, C₂-C₁₀-Alkenyloxyimino-(C₁-C₈)-alkyl, C₂-C₁₀-Alkinyloxyimino-(C₁-C₈)-alkyl, C₂-C₁₀-Alkinylcarbonyl, C₃-C₆-Cycloalkylcarbonyl, oder ein fünf-, sechs-, sieben-, acht-, neun- oder zehngliedriger gesättigter, teilweise ungesättigter oder aromatischer Heterocyclus enthaltend ein, zwei, drei oder vier Heteroatome aus der Gruppe O, N und S;
R^Φ Wasserstoff, C₁-C₄-Alkyl, C₁-C₂-Halogenalkyl, C₁-C₄-Alkoxy, C₂-C₄-Alkenyloxy, C₂-C₄-Alkinyloxy; wobei die Gruppen R^Φ durch eine, zwei oder drei gleiche oder verschiedene Gruppen R^b substituiert sein können wie oben definiert;
n null, 1 oder 2;
m 1, 2, 3 oder 4;
und landwirtschaftlich annehmbare Salze davon.The present invention relates to pyridazines of the formula I.

in which the substituents have the following meanings:
R ¹ , R ^{4 are} independently halogen, cyano or C ₁ -C ₈ alkoxy;
R ^{2 is} C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₂ -C ₁₀ -haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkenyl, C ₃ -C ₁₂ cycloalkenyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₁₂ halocycloalkenyl, aryl or aromatic heterocycle containing besides carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, wherein the aromatic groups are five-, six-, seven-, eight-, nine- or ten-membered ring systems; and R ² may contain one, two, three or four identical or different groups R ^a , which are independently selected from:
R ^a cyano, nitro, hydroxy, carboxyl, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl, C ₁ -C ₆ -alkoxy, C ₂ -C ₆ -alkenyloxy, C ₃ -C ₆ -alkynyloxy, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkenyloxy, c (O) R ^Π , C (o) OR ^Π , C (S) OR ^Π , C (O) SR ^Π , C (S) SR ^Π , OC (O) OR ^Π , C ₁ -C ₆ -alkylthio, amino, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ - alkylamino, C ₁ -C ₆ -alkylene, oxy-C ₁ -C ₈ -alkylene, oxy-C ₁ -C ₃ -alkyleneoxy, where divalent groups may be attached to the same atom or to adjacent atoms, phenyl, naphthyl, five -, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing in addition to carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members;
R ^Π C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkenyl;
where the aliphatic, alicyclic or aromatic groups in the abovementioned groups R ^a and R ^{Π are in} turn partially or completely halogenated and / or may carry one, two or three groups R ^b :
R ^{b is} halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, Aminocarbonyl, aminothiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, wherein the alkyl groups in these groups contain 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these groups contain 2 to 8 carbon atoms; Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl-C ₁ -C ₆ -alkoxy, aryl-C ₁ -C ₆ -alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members, the hetaryl radicals contain 5 or 6 ring members, wherein the cyclic systems may be partially or completely halogenated and / or substituted by alkyl or haloalkyl groups;
R ^{3 is} aryl or heteroaryl containing, in addition to carbon atoms, one to four nitrogen atoms or zero to two nitrogen atoms and one sulfur or oxygen atom as ring members, the groups being five-, six-, seven-, eight-, nine- or ten-membered ring systems which in addition to a group L ¹ in ortho position to the bond to the pyridazine skeleton, at least one further group
L _{m can} carry:
L ^{1 is} halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl;
L is halogen, hydroxy, cyanato (OCN), cyano, nitro, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -halocycloalkyl, C ₃ -C ₆ -cycloalkenyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -haloalkoxy, C ₂ -C ₁₀ - Alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkenyloxy, amino, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ ) alkylamino, C ( O) -R ^Φ , C (S) -R ^Φ , S (O) _n -R ^Φ ; C ₁ -C ₈ alkoxyimino (C ₁ -C ₈ ) alkyl, C ₂ -C ₁₀ alkenyloxyimino (C ₁ -C ₈ ) alkyl, C ₂ -C ₁₀ alkynyloxyimino (C ₁ -C ₈ ) -alkyl, C ₂ -C ₁₀ -alkynylcarbonyl, C ₃ -C ₆ -cycloalkylcarbonyl, or a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S;
R ^{Φ is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyloxy, C ₂ -C ₄ -alkynyloxy; wherein the groups R ^Φ may be substituted by one, two or three identical or different groups R ^b as defined above;
n is zero, 1 or 2;
m is 1, 2, 3 or 4;
and agriculturally acceptable salts thereof.

Moreover, the invention relates to processes and intermediates for the preparation of these Verbindun conditions, agents containing them and their use for controlling phytopathogenic harmful fungi. In addition, the invention relates to the use of pyrazines for the manufacture of a medicament for the treatment of cancer.

Out WO 2005/121104 and WO 2006/045192 are known 3,6-dimethyl-4,5-diphenylpyridazine, or 3-chloro-o-methyl-4,5-diphenylpyridazine with fungicidal action. Individual 3,6-dichloro-4,5-diphenylpyridazines and 3,6-dichloro-4-methyl-5-phenylpyri dazine are in WO 2005/063762 , J. Org. Chem. Vol. 29, pp. 2128-35 (1964), J. Chem. Soc., P. 1316 (1970).

The fungicidal action of the known compounds is in many cases especially at low application rates, not satisfactory. On this basis, the present invention is based on the object Compounds with improved activity and / or broadened spectrum of activity provide.

Accordingly, the compounds defined above were found. Furthermore have been methods and intermediates for their preparation, they containing agents and methods for controlling harmful fungi using the compounds I found.

The Compounds of the formula I according to the invention can be be obtained in different ways.

Pyridazines of the formula I in which both groups R ¹ and R ^{4 are} halogen, in particular chlorine, are advantageously accessible by halogenation of the compounds of the formula II with a halogenating agent [HAL] in the following way. They correspond to the formula I.1 in which Hal represents halogen, preferably bromine or chlorine, in particular chlorine.

This reaction is usually carried out at temperatures of 0 to 150 ° C or preferably from 80 to 125 ° C, in bulk or in an inert organic solvent [see. Bioorg Med Chem Lett, 2003, 13, 1581 ; J Chem Soc, 1970, 1316 ]. Preferred halogenating agents are chlorinating or brominating agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride, in particular phosphorus oxychloride. The reaction may be carried out neat or in the presence of a solvent.

The Halogenating agent is generally in equimolar Quantities used. It can also be in excess or be used as a solvent.

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide. It can too Mixtures of said solvents can be used.

The 3,6-Dihydroxypyridazinder Formula II are preferred by reaction of furandions of formula III with hydrazine or hydrazine hydrate receive.

This reaction is usually carried out at temperatures of -30 ° C to 150 ° C, preferably 50 ° C to 120 ° C, in an inert organic solvent or in suitable inorganic or organic acids and water instead [cf. Eur J Org Chem, 2004, 2797-2804 ; J Chem Soc, 1970, 1316 ; WHERE 2006/032518 ; Heteroatom Chem, 16 (4), 298-307, 2005 ; Helv Chim Acta, 85 (7), 2195-2213, 2002 ].

suitable Solvents are ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol. It is also possible to use mixtures of the solvents mentioned be used.

When Acids find inorganic acids like hydrofluoric acid, Hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, as well as organic acids such as Formic acid, acetic acid, propionic acid, Oxalic acid, toluenesulfonic acid, benzenesulfonic acid, Camphorsulfonic acid, citric acid and trifluoroacetic acid Use.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield, hydrazine or hydrazine hydrate in an excess of bis to use 5 molar equivalents based on III.

The Furandions of the formula III are advantageous by oxidative cyclization obtained from esters of formula IV.

This reaction is usually carried out at temperatures from -30 ° C to + 100 ° C, preferably + 10 ° C to + 50 ° C, in an inert organic solvent in the presence of a base [cf. Synlett, 2002, (6), 947-951 ; Bioorg Med Chem Lett, 2003, 13, 1195 ]. As the oxidizing agent is, for example, oxygen in question.

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably nitriles such as acetonitrile and propionitrile. It can also mixtures of said solvents can be used.

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) into consideration. Particularly preferred is DBU. The bases are in general used in catalytic amounts, but they can also be equimolar, in excess or optionally as solvent be used.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield that Base in about 3 molar equivalents based on IV use.

The Esters of formula IV are by condensation of carboxylic acids of the formula V or their sodium or potassium salts, with halides of the formula VI in which X is a halogen, such as iodine, chlorine or bromine, preferably chlorine or bromine, available.

This reaction is usually carried out at temperatures of -50 ° C to 100 ° C, preferably 25 ° C to 100 ° C, in an inert organic solvent in the presence or absence of a base [see. Bioorg Med Chem Lett, 2003, 13, 1195 ; Synth. Commun., 25 (12), 1681-1686, 2005 . Org Prep and Proc. Int., 20 (5), 527-532, 1988 ; Synth Commun, 16 (14), 1777-1780, 1986 ].

suitable Solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably acetonitrile. It can also be mixtures of the above Solvent can be used.

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, di-isopropylethylamine, trisdioxaheptylamine (TDA) and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, Lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are bases such as potassium carbonate and TDA.

The Bases are generally used in catalytic amounts, but they can also be equimolar, in excess or optionally used as a solvent.

halides of the formula VI in which X is a halogen, such as iodine, bromine or chlorine, especially chlorine or bromine, are by halogenation accessible from ketones of formula VII.

This reaction is usually carried out at temperatures of -78 ° C to 100 ° C, preferably 25 ° C to 80 ° C, in an inert organic solvent or in an acid [cf. JACS, 1997, 119, 2453-2463 ; Synthesis (2), 143-146, 1980 ; JACS, 1208 (8), 2558-2570, 2006 ]. Preferred halogenating agents are elemental halogen, such as chlorine or bromine, in particular bromine, or other common halogenating agents, such as N-bromosuccinimide, thionyl chloride, sulfuryl chloride, Cu (2) bromide or benzyltrimethylammonium tribromide.

suitable Solvents are ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), particularly preferably THF or halogenated hydrocarbons such as Methylene chloride, chloroform and carbon tetrachloride, but also other solvents such as, for example, ethyl acetate.

When Acids find organic acids like formic acid, Acetic acid, propionic acid, oxalic acid, Toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, Citric acid and trifluoroacetic acid use. It may also be mixtures of said solvents be used.

Compounds of the formula I in which both groups R ¹ and R ^{4 are} halogen, in particular chlorine, and R ^{2 is} an aliphatic group, are alternatively accessible from furandions of the formula III which are obtained from the reaction of α-ketocarboxylic acids or their activated derivatives , such as B. esters of formula VIII, in which R is C ₁ -C ₄ -alkyl, such as methyl or ethyl, are obtainable with carboxylic anhydrides of the formula IX.

This reaction is usually carried out at temperatures of 0 ° C to 150 ° C, preferably 0 ° C to 50 ° C, in an inert organic solvent in the presence of a base and a catalyst [see. Tetrahedron Lett, 47 (2006), 2107-2109 ].

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, 1,2-dichloroethane, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethylsulfoxide, dimethylformamide and Dimethylacetamide, more preferably dichloromethane. It can also mixtures of said solvents can be used.

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, Pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Especially preferred is tributylamine. The bases are generally used in catalytic amounts, but they can also be equimolar, in excess or optionally used as a solvent.

When Acids and acid catalysts find Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, tin IV chloride, Titanium-IV-chloride and zinc-II-chloride, preferably titanium-IV-chloride Use.

α-Ketocarbonsäureester of formula VIII are preferably accessible under Grignard conditions from the corresponding (hetero) aryl halides, in particular (hetero) aryl bromides R ³ -X of the formula X in which X is halogen, such as chlorine or bromine, especially bromine, and the corresponding oxalic acid dialkyl esters of the formula XI, in particular diethyl oxalate.

This reaction is carried out in the first step usually at temperatures of -100 ° C to 0 ° C, preferably -80 ° C to -20 ° C, in bulk or an inert organic solvent in the presence of a Grignard reagent or in the presence of magnesium [cp , Lit. Synlett, (6), 885-887, 2003 ; J Med Chem, 49 (4), 1271-1281, 2006 ]. Preferred Grignard salts are C ₁ -C ₄ -alkylmagnesium chlorides, in particular isopropylmagnesium chloride.

Suitable solvents are the oxalic acid of formula XI, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as Methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferred are ethers such as diethyl ether or THF. It is also possible to use mixtures of the solvents mentioned.

The reaction of the Grignard compound formed in the first step with the oxalic acid esters is usually carried out at temperatures of from -78 ° C. to + 100 ° C., preferably + 10 ° C. to + 50 ° C., in an inert organic solvent [cf. Lit. J Med Chem, 49, (4), 1271-1281, 2006 ; JOC, 68 (10), 3990-3998, 2003 ].

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferred are ethers such as diethyl ether or THF and aliphatic Hydrocarbons such as hexane. It can also be mixtures the said solvents are used.

Furthermore, the α-ketocarboxylic esters of the formula VIII can be prepared directly from oxalic esters of the formula XI and the corresponding aryl halides of the formula X in the presence of a base [cf. JACS, 125 (30), 9032-9034, 2003 ; Synthesis, 9, 1241-1242, 1998 ]

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, most preferably butyl lithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal alcoholates, such as sodium methoxide, Sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, also organic bases, eg. B. tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines. The bases are generally used in catalytic amounts, but they can also be equimolar, in excess or optionally used as a solvent.

Compounds of the formula I in which one group of R ¹ and R ^{4 is} alkoxy and the other group is halogen, in particular chlorine, correspond to the formula I.2 or I.3. They are accessible by reacting the compounds of formula I.1 with the corresponding alkoxide [Y ^- - ^- M ⁺ ].

This reaction is usually carried out at temperatures of 0 ° C to 120 ° C, preferably 25 ° C to 100 ° 0, in an inert organic solvent [see. Tetrahedron, 60 (36), 7983-7994, 2004 ; Synthesis, (7), 1163-1168, 1999 ].

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, especially methanol. It can also mixtures of said solvents can be used.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Y ⁺ M ^- in excess relative to I.1.

Compounds of the formula I in which both groups R ¹ and R ^{4 are} alkoxy correspond to the formula I.4. They are accessible by reacting the compounds of the formula I.1 with the corresponding alkoxide [Y ⁺ M ^- ], where M is a cation, usually an alkali metal or alkaline earth metal cation.

This reaction is usually carried out at temperatures of 0 ° C to 120 ° C, preferably 25 ° C to 100 ° C, in an inert organic solvent [cf. Helv. Chim. Acta, 37, 121-33; 1954 ; Chem. & Pharm. Bull., 13 (5), 586-93; 1965 ].

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, especially methanol. It can also mixtures of said solvents can be used.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Y ⁺ M ^- in an excess based on 1.1.

Compounds of the formula I in which one group of R ¹ and R ^{4 is} cyano and the other group is halogen, in particular chlorine, or both groups of R ¹ and R ^{4 are} cyano, correspond to the formulas I.5, I .6 or I.7. They are accessible according to the selected boundary conditions from compounds of formula I.1 by reaction with cyanides.

This reaction is usually carried out at temperatures of from 50 ° C. to 150 ° C., preferably from 80 ° C. to 100 ° C., in an inert organic solvent, if appropriate in the presence of a catalyst, such as sodium p-toluenesulfonic acid [cf. Heterocycles, 39 (1), 345-56; 1994 ]. Usually come here alkali or Erdalkalicyanide, preferably potassium cyanide in question.

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably dimethylformamide. It can also be mixtures of mentioned solvents are used.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield that Cyanide in excess relative to I.1 use.

alternative are the compounds of formula I by oxidation of 4,5-dihydropyridazines the formula XII accessible.

The oxidation is usually carried out at temperatures of 20 ° C to 100 ° C, preferably 40 ° C to 80 ° C, in an inert organic solvent in the presence of an oxidizing agent and / or a catalyst, such as preferably Pt or Pd or oxides or peroxides, such as H ₂ O ₂ [Lit .: Coprehensive Organic Reactions, RC Larock, Chapter 5.1 Aromatization - Dehydrogenation, page 93, VCH, 1989 ; J Het, Chem, 26 (3), 717-719, 1989 ].

response times are usually from 1 to 48 hours. Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ethers, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, Chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethylsulfoxide, dimethylformamide and dimethylacetamide. It can also mixtures of said solvents can be used.

The Oxidizing agent is usually in equimolar Quantities, based on the compound of formula XII used. It may be advantageous for the yield, the oxidizing agent in equimolar amounts or in an excess of use up to 5 molar equivalents based on XII.

Furthermore, dihydropyridazines can be obtained by chlorination or bromination and subsequent elimination of HCl or HBr. This reaction is usually carried out at temperatures from -30 ° C to 100 ° C, preferably 0 ° C to 80 ° C, in an inert organic solvent or in organic acids such as acetic acid [cf. Lit. Synthesis, 1995, (10), 240-242 ; Syn Comm, 23 (21), 2957-2964, 1993 ].

4.5-dihydropyridazines of the formula XII are advantageous from 1,2-diketones of the formula XIII accessible by reaction with hydrazine or hydrazine hydrate.

This reaction is usually carried out at temperatures from -30 ° C to 100 ° C, preferably 0 ° C to 80 ° C, in an inert organic solvent [cf. Lit. Syn Comm, 31 (5), 645-651, 2001 ; Heterocycles, 57 (1), 39-46, 2002 ].

suitable Solvents are ethers, such as diethyl ether, diisopropyl ether, Dimethoxyethane, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, more preferably alcohols. It can also mixtures of said solvents can be used.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield, hydrazine or hydrazine hydrate in an excess of bis to use 5 molar equivalents based on XIII.

diketones of formula XIII can be prepared by reacting compounds of the formulas XIV and V via the intermediate XIIIa become.

The reaction of the compounds XIV and XV is usually carried out at temperatures from -30 ° C to 100 ° C, preferably 20 ° C to 40 ° C, in bulk or in an inert organic solvent [cf. Lit. Tetrahedron, 45 (17), 5667-5678, 1989 ].

Prefers the reaction is carried out in bulk.

The reaction of the intermediate XIIIa is usually carried out at temperatures of -30 ° C to 80 ° C, preferably 0 ° C to 30 ° C, in an aqueous organic solvent, in an acidic medium, preferably at a pH of about 2 [see. Lit. Tetrahedron, 45 (17), 5667-5678, 1989 ; Tetrahedron, 45 (7), 2099-2108, 1989 ,

suitable Solvents are water and ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferably ethanol. It can also be mixtures of mentioned solvents are used.

When Acids and acid catalysts find inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, Sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, tin IV chloride, Titanium-IV-chloride and zinc-II-chloride, as well as organic acids such as formic acid, acetic acid, propionic acid, Oxalic acid, toluenesulfonic acid, benzenesulfonic acid, Camphorsulfonic acid, citric acid and trifluoroacetic acid, prefers hydrochloric acid use.

The Acids are generally used in catalytic amounts, but they can also be equimolar, in excess or optionally used as a solvent.

alternative For example, the compounds of formula I can be obtained from substituted hydrazonoketones of the formula XVI.

This reaction is usually carried out at temperatures of 0 ° C to 120 ° C, preferably 50 ° C to 100 ° C, in an inert organic solvent in the presence of a base [cf. Lit. J Chem Res, 3, 187-189, 2005 ].

suitable Solvents are ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dimethoxyethane, dioxane, anisole and tetrahydrofuran, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, more preferably ethanol. It can also mixtures of said solvents can be used.

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred teritäre amines such. B. triethylamine.

The Bases are generally used in catalytic amounts, but they can also be equimolar, in excess, preferably up to 2 molar equivalents, or optionally as Solvent can be used.

The Hydrazonoketones of the formula XVI are by reaction of compounds of the formulas XVII and XVIII available.

This reaction is usually carried out at temperatures of 0 ° C to 150 ° C, preferably 20 ° C to 120 ° C, in an inert organic solvent in the presence or absence of a base or an acidic catalyst [cf. Lit. J for Prakt Chem, 328 (4), 551-557, 1986 ; J for Prakt Chem, 327 (1), 109-116, 1985 ; Synthesis, (5), 691-694, 2003 ].

suitable Solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, benzene, more preferably benzene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, more preferably dichloromethane, ethers, such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, particularly preferably dioxane, nitriles such as acetonitrile and propionitrile, Ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethylsulfoxide, dimethylformamide and Dimethylacetamide, more preferably dimethylformamide. It can also mixtures of said solvents can be used.

When Acids and acid catalysts find inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, Sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, tin IV chloride, Titanium-IV-chloride and zinc-II-chloride, as well as organic acids such as formic acid, acetic acid, propionic acid, Oxalic acid, citric acid, trifluoroacetic acid and sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, Camphorsulfonic acid, more preferably p-toluenesulfonic acid, Use. The acids are generally in catalytic Quantities, preferably 0.001 to 0.05 molar equivalents on XVIII, but they can also be equimolar, in excess or optionally as solvent be used.

When Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred Alkalimetalhydrogencarbonate such as sodium bicarbonate.

The Bases are generally used in catalytic amounts, but they can also be equimolar, in excess, preferably up to 2 molar equivalents, or optionally as Solvent can be used.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield, XVII in about 0.8 to 1.3 molar equivalents based on XVIII use.

The Hydrazonoketones of the formula XVIII are from reaction of diketones of formula XIX with hydrazine or hydrazine hydrate accessible.

This reaction is usually carried out at temperatures from -30 ° C to 120 ° C, preferably 0 ° C to 80 ° C, in an inert organic solvent [cf. Lit. J Med Chem, 48 (22), 6843-6854, 2005 ].

suitable Solvents include alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and t-butanol, especially preferably ethanol.

It may also be mixtures of said solvents be used.

The Starting materials are generally in equimolar amounts with each other implemented. It may be advantageous for the yield that Hydrazine or hydrazine hydrate in molar ratio of 0.8 to 1.3 based on XIX use.

The required starting materials are known in the literature or can be prepared according to the cited literature become.

The Reaction mixtures are worked up in the usual way, z. B. by mixing with water, separation of the phases and optionally Chromatographic purification of the crude products. The intermediate and final products fall z. T. in the form of colorless or pale brownish, Toughened oils, which under reduced pressure and at moderately elevated temperature of volatile Shares are freed or cleaned. Unless the intermediate and Final products can be obtained as solids, cleaning can also by recrystallization or digestion.

Provided individual compounds I not to those described above Because they are accessible, they can by derivatization other compounds I are produced.

Provided However, in general, isomer mixtures are obtained in the synthesis a separation is not essential, since the individual Isomers partially during processing for the application or in the application (eg under light, acid or base action) can be converted into each other. Appropriate Transformations can also be made after the application, for example in the treatment of plants in the treated plant or take place in the harmful fungus to be controlled.

• – nicht-aromatisches gesättigte oder teilweise ungesättigtes 5- oder 6-gliedriges Heterocyclyl, enthaltend ein bis drei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome, z. B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-Isoxazolidinyl, 4-Isoxazolidinyl, 5-Isoxazolidinyl, 3-Isothiazolidinyl, 4-Isothiazolidinyl, 5-Isothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thiazolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-Imidazolidinyl, 4-Imidazolidinyl, 2-Pyrrolin-2-yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 1,3–Dioxan-5-yl, 2-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydrothienyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl und 2-Piperazinyl;
• – 5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z. B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 2-Imidazolyl, 4-Imidazolyl, und 1,3,4-Triazol-2-yl;
• – 6-gliedriges Heteroaryl, enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoffatome als Ringglieder enthalten können, z. B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl und 2-Pyraziyl;

Alkylen: divalente unverzweigte Ketten aus 2 bis 8 CH₂-Gruppen, z. B. CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂CH₂ und CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂;
Oxyalkylen: divalente unverzweigte Ketten aus 2 bis 4 CH₂-Gruppen, wobei eine Valenz über ein Sauerstoffatom an das Gerüst gebunden ist, z. B. OCH₂CH₂, OCH₂CH₂CH₂ und OCH₂CH₂CH₂CH₂;
Oxyalkylenoxy: divalente unverzweigte Ketten aus 1 bis 3 CH₂-Gruppen, wobei beide Valenzen über ein Sauerstoffatom an das Gerüst gebunden ist, z. B. OCH₂O, OCH₂CH₂O und OCH₂CH₂CH₂O;In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for. C ₁ -C ₆ alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 Methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above: in particular C ₁ -C ₂ -haloalkyl, such as chloromethyl, Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- Chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, for. C ₂ -C ₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3 Methyl 3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2- propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2 Dimethyl 2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2.2 Dimethyl 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3.3 Dimethyl 2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-prope nyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for. B. C ₂ -C ₆ alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3 Pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1 Ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-Dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1- Ethyl 2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Cycloalkyl: mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, e.g. C ₃ -C ₈ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
Aryl: mono-, bi- or tricyclic aromatic hydrocarbon groups containing 6, 8, 10, 12 or 14 ring members, such as phenyl, naphthyl or anthracenyl, preferably phenyl or naphthyl, in particular phenyl;
A five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S:

• Non-aromatic saturated or partially unsaturated 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrroline-2 yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2- Tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
• 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups, which besides carbon atoms may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members , z. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl;
• 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, for. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;

Alkylene: divalent unbranched chains of 2 to 8 CH ₂ groups, e.g. CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ and CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ;
Oxyalkylene: divalent unbranched chains of 2 to 4 CH ₂ groups, wherein a valence is bonded to the skeleton via an oxygen atom, for. OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ and OCH ₂ CH ₂ CH ₂ CH ₂ ;
Oxyalkylenoxy: divalent unbranched chains of 1 to 3 CH ₂ groups, wherein both valences are bonded via an oxygen atom to the skeleton, z. OCH ₂ O, OCH ₂ CH ₂ O and OCH ₂ CH ₂ CH ₂ O;

According to the present Invention come as agriculturally acceptable salts especially the salts of those cations or the acid addition salts those acids whose cations or respectively Anions the pesticidal effect of the invention Do not negatively affect pyrimidines.

Thus, as cations in particular the ions of the alkali metals, preferably sodium or potassium, the alkaline earth metals, preferably calcium, magnesium or barium, the transition metals, preferably manganese, copper, zinc or iron, or the ammonium ion, the desired one to four (C ₁ - C ₄ ) -alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri- (C ₁ -C ₄ ) -alkylsulfonium and sulfoxonium ions, preferably tri (C ₁ -C ₄ ) -alkylsulfoxonium, into consideration.

Anions of advantageously usable acid addition salts are, for example, chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, car carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of (C ₁ -C ₄ ) -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reaction of the compounds according to the invention with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

In The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of formula I, which have chiral centers.

By hindered rotation of unsymmetrically substituted groups Atropisomers of compounds of formula I are present. They are too Subject of the invention.

The Embodiments of intermediates relating to Variables correspond to those of the formula I.

With regard to their intended use of the pyridazines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:
One embodiment relates to compounds I in which R ¹ and R ^{4 are} halogen, in particular chlorine. These compounds correspond to the formula I.1.

A further embodiment relates to compounds I in which R ^{1 is} halogen, in particular chlorine and R ^{4 is} C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, in particular methoxy. These compounds correspond to the formula I.2.

A further embodiment relates to compounds I in which R ^{1 is} C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, in particular methoxy, and R ^{4 is} halogen, in particular chlorine. These compounds correspond to the formula I.3.

A further embodiment relates to compounds I in which R ¹ and R ^{4 are} each C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, in particular methoxy. These compounds correspond to the formula I.4.

A further embodiment relates to compounds I in which R ^{1 is} halogen, in particular chlorine and R ^{4 is} cyano. These compounds correspond to the formula I.5.

Another embodiment relates to compounds I in which R ^{1 is} cyano and R ^{4 is} halogen, esp special chlorine stands. These compounds correspond to the formula I.5.

Another embodiment relates to compounds I in which R ¹ and R ^{4 are} cyano. These compounds correspond to the formula I.7.

In the compounds according to the invention, R ^{2 is} preferably C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₂ C ₁₀ haloalkynyl, C ₃ -C ₁₂ cycloalkyl (including in particular C ₃ -C ₅ cycloalkyl and / or C ₉ -C ₁₂ cycloalkyl), C ₃ -C ₁₂ halocycloalkyl, C ₃ -C ₁₂ cycloalkenyl , C ₃ -C ₁₂ -halocycloalkenyl, naphthyl or halonaphthyl; or a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic carbon-bonded heterocycle containing one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur, more preferably C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl , C ₂ -C ₁₀ haloalkynyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ halocycloalkyl, C ₃ -C ₁₂ cycloalkenyl or C ₃ -C ₁₂ halocycloalkenyl or a five, six, seven , eight, nine o the ten-membered saturated, partially unsaturated or aromatic carbon-bonded heterocycle containing one, two, three or four heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur; wherein R ² may contain one, two, three or four identical or different groups R ^a as defined herein.

One embodiment relates to compounds I in which R ^{2 is} an aliphatic group which is unsubstituted or, as defined above ^, substituted by R ^a . These compounds correspond to formula Ia

One embodiment of the compounds Ia relates to those in which R ^{2 is} C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ - Alkynyl, C ₂ -C ₁₀ haloalkynyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ halocycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₃ -C ₁₂ halocycloalkenyl.

One embodiment relates to compounds Ia in which R ^{2 is} C ₁ -C ₈ -alkyl, in particular branched C ₃ -C ₈ -alkyl, C ₁ -C ₆ -haloalkyl, C ₃ -C ₈ -alkenyl, in particular branched C ₃ - C ₈ alkenyl, C ₃ -C ₆ cycloalkyl which may have a C ₁ -C ₄ alkyl group, or C ₅ -C ₆ cycloalkenyl which may have a C ₁ -C ₄ alkyl group.

A further embodiment relates to compounds Ia in which R ² is C ₃ -C ₁₂ -cycloalkyl, in particular C ₆ -C ₈ -cycloalkyl.

A further embodiment relates to compounds Ia, in which R ² is C ₁ -C ₁₀ -alkyl, in particular C ₃ -C ₈ -alkyl, which is optionally substituted by one, two or three R ^a . R ^a is preferably selected from halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -alkoximino , C ₂ -C ₆ -alkenyloximino, C ₂ -C ₆ -alkynyloximino, C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, where the aliphatic and / or alicyclic groups are in turn represented by one, two or three groups R ^b can be substituted. In this case, R ^{b is} preferably independently halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylcarbonyl or C ₁ -C ₆ -haloalkylcarbonyl.

According to one embodiment of this embodiment, R ^{2 is} C ₁ -C ₁₀ -haloalkyl, in particular C ₃ -C ₈ -haloalkyl.

A further embodiment relates to compounds Ia in which R ^{2 is} C ₂ -C ₁₀ alkenyl, in particular C ₃ -C ₈ alkenyl, which is optionally substituted by one, two or three R ^a , as defined herein.

A further embodiment relates to compounds Ia in which R ^{2 is} C ₂ -C ₁₀ -alkynyl, in particular C ₃ -C ₈ -alkynyl, which is optionally substituted by one, two or three R ^a , as defined herein.

A further embodiment relates to compounds Ia in which R ^{2 is} C ₃ -C ₁₂ -cycloalkenyl, in particular C ₅ -C ₁₀ -cycloalkenyl, especially C ₅ - or C ₆ -cycloalkenyl, which optionally substituted by one, two or three R ^a is as defined herein. According to one embodiment of this embodiment of the invention, the Cycoalkenylgruppe is one, two or three times by C ₁ -C ₄ alkyl, such as. As methyl and / or ethyl substituted.

One embodiment relates to compounds I in which R ^{2 is} a five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle bonded via carbon to the pyridazine skeleton, containing one, two, three or four Heteroatoms from the group consisting of oxygen, nitrogen and sulfur, wherein the heterocycle is unsubstituted or substituted by one, two, three or four identical or different substituents R ^a as defined herein. These compounds correspond to the formula IB According to a preferred embodiment of this embodiment, R ^{2 is} a substituted or unsubstituted five- or six-membered saturated or aromatic heterocycle bonded via carbon to the pyridazine skeleton.

When R ² carries one, two, three or four, preferably one, two or three, identical or different groups R ^a , R ^{a is} preferably selected from halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoximino, C ₂ -C ₆ alkenyloximino, C ₂ -C ₆ alkynyloximino , C ₃ -C ₆ -cycloalkyl, C ₅ -C ₆ -cycloalkenyl, wherein the aliphatic or alicyclic groups in turn may be partially or fully halogenated or carry one, two or three groups R ^b .

If R ^a carries at least one group R ^b , then R ^{b is} preferably selected from halogen, cyano, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ Alkynyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl and C ₂ -C ₆ alkoxy.

According to a preferred embodiment of the invention, R ^{2 is} C ₁ -C ₁₀ -alkyl, in particular C ₃ -C ₈ -alkyl, which is optionally substituted by one, two or three R ^a . R ^a is preferably selected from halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -alkoximino , C ₂ -C ₆ -alkenyloximino, C ₂ -C ₆ -alkynyloximino, C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, where the aliphatic and / or alicyclic groups are in turn represented by one, two or three groups R ^b can be substituted. In this case, R ^{b is} preferably independently halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylcarbonyl or C ₁ -C ₆ -haloalkylcarbonyl. According to one embodiment of this embodiment, R ^{2 is} C ₁ -C ₁₀ -haloalkyl, in particular C ₃ -C ₈ -haloalkyl.

A further embodiment relates to compounds I in which R ^{2 is} an aryl group which is unsubstituted or substituted as defined above by R ^a , such as phenyl or naphthyl, in particular a phenyl group. These compounds correspond to formula Ib Preferred compounds of formula Ib in position R ^{2 have} a group selected from phenyl, 3-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3-hydroxyphenyl, 4 Hydroxyphenyl, 3-tolyl and 4-tolyl.

A further embodiment relates to compounds I in which R ^{2 is} a heteroaryl group bonded via carbon which is unsubstituted or substituted by R ^a as defined above. These compounds correspond to formula Ic Preferred compounds of the formula Ic have, in position R ^2, a group selected from pyridin-3-yl and pyridin-4-yl.

Another embodiment relates to compounds I in which R ^{2 is} a nitrogen-bonded heteroaryl group which is unsubstituted or substituted as defined above, by R ^a . These compounds correspond to Formula Id

In one embodiment, R ^{2 is} not optionally substituted phenyl.

In another embodiment, R ^{2 is} not C ₃ -C ₈ cycloalkyl, more preferably not C ₃ -C ₁₂ cycloalkyl. Preferably, R ^{2 is} not C ₆ -C ₈ cycloalkyl, more preferably not C ₃ -C ₁₂ cycloalkyl.

According to a further preferred embodiment of the invention, R ^{2 is} C ₂ -C ₁₀ alkenyl, in particular C ₃ -C ₈ alkenyl, which is optionally substituted by one, two or three R ^a , as defined herein.

According to a further preferred embodiment of the invention, R ^{2 is} C ₂ -C ₁₀ -alkynyl, in particular C ₃ -C ₈ -alkynyl, which is optionally substituted by one, two or three R ^a , as defined herein.

According to a further preferred embodiment of the invention, R ^{2 is} C ₃ -C ₁₂ -cycloalkenyl, in particular C ₅ -C ₁₀ -cycloalkenyl, especially C ₅ - or C ₆ -cycloalkenyl, which is optionally substituted by one, two or three R ^a , as defined herein. According to one embodiment of this embodiment of the invention, the Cycoalkenylgruppe is one, two or three times by C ₁ -C ₄ alkyl, such as. As methyl and / or ethyl substituted.

According to a further preferred embodiment of the invention, R ^{2 is} a saturated, partially unsaturated, unsaturated or aromatic heterocycle bonded via carbon to the pyridazine skeleton containing five, six, seven, eight, nine or ten members containing one, two, three or ten four heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, wherein the heterocycle is unsubstituted or substituted by one, two, three or four identical or different substituents R ^a as defined herein.

A further embodiment relates to compounds I in which R ^{3 is} an aryl group which is unsubstituted or as defined above ^, substituted by R ^a , such as phenyl or naphthyl, in particular a phenyl group. These compounds correspond to formula IA

In one embodiment of the compounds IA, R ^{3 is} phenyl which, in addition to a group L ¹ in the ortho position to the bond to the pyridazine backbone, carries at least one further group L _m .

In a further embodiment of the compounds IA, R ^{3 is} phenyl which is substituted by only one group L ¹ in ortho position to the bond to the pyridazine backbone.

In a further embodiment of the compounds IA, R ^{3 is} phenyl which, in addition to two groups L ^1, carries at least one further group L _m in both ortho positions to the bond to the pyridazine skeleton.

In a further embodiment of the compounds IA, R ^{3 is} phenyl, which is substituted by only two groups L ¹ in both ortho positions to the bond to the Pyridazingrundgerüst.

A further embodiment relates to compounds I in which R ^{3 is} a heteroaryl group bonded via carbon, which is unsubstituted or substituted by R ^a as defined above. These compounds correspond to Formula IB

A further embodiment relates to compounds I in which R ^{3 is} a nitrogen-bonded heteroaryl group which is unsubstituted or substituted as defined above, by R ^a . These compounds correspond to formula IC

L _m is preferably each independently selected from the preferred meanings given herein for L _m , it being further preferred that L is selected from halo, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl , in particular C ₁ -C ₂ -fluoroalkyl, C ₁ -C ₄ -alkoxy and C ₁ -C ₄ -alkoxycarbonyl, more preferably selected from nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, trifluoromethyl, fluoromethyl, Methoxy and methoxycarbonyl. Preferred L in the ortho position are fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, in particular methyl or ethyl, C ₁ -C ₂ -fluoroalkyl such as trifluoromethyl, and C ₁ -C ₄ -alkoxy, in particular methoxy or ethoxy.

• – Halogen, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl;
• – jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen;
• – jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen;
• – jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
• – jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
• – jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 11 gleichen oder verschiedenen Halogenatomen;
• – jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkylcarbonyloxy, Alkoxycarbonyl, Alkylsulfonyloxy, Hydroximinoalkyl oder Alkoximinoalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen; Cycloalkyl mit 3 bis 6 Kohlenstoffatomen,
• – in 2,3-Position verknüpftes 1,3-Propandiyl, 1,4-Butandiyl, Methylendioxy (-O-CH₂-O-) oder 1,2-Ethylendioxy (-O-CH₂-CH₂-O-), wobei diese Gruppen einfach oder mehrfach, gleichartig oder verschieden substituiert sein können durch Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen.

Further preferably, the substituents L, which are bonded to R ³ = heteroaryl, as explained below, or R ³ = phenyl, independently of one another are

• - halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
• - in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl having in each case 1 to 6 carbon atoms;
• - in each case straight-chain or branched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms;
• - in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or halogenoalkylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
• - in each case straight-chain or branched haloalkenyl or haloalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
• - in each case straight-chain or branched haloalkenyl or haloalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;
• - in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in the individual alkyl moieties; Cycloalkyl of 3 to 6 carbon atoms,
• 2,3-propanediyl, 1,4-butanediyl, methylenedioxy (-O-CH ₂ -O-) or 1,2-ethylenedioxy (-O-CH ₂ -CH ₂ -O-) linked in the 2,3-position where these groups may be mono- or polysubstituted by identical or different substituents by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

In particular, the following groups are suitable for L _m : halogen, such as fluorine or chlorine; cyano; nitro; alkoxycarbonyl; C ₁ -C ₄ alkyl, such as methyl; C ₁ -C ₄ -haloalkyl, such as trifluoromethyl; C ₁ -C ₄ alkoxy, such as methoxy.

In one embodiment, L _{m is} on the phenyl group in position 4.

Another embodiment relates to groups R ³ , which are substituted by chlorine in addition to a group 1 ¹ .

In one embodiment, the phenyl group substituted by L ¹ and L _{m is} one of the following substituent combinations: 2-fluoro-6-chloro, 2,6-difluoro, 2,6-dichloro, 2-fluoro-6-methyl, 2,4 , 6-trifluoro, 2,6-difluoro-4-methoxy, 2-chloro-4-methoxy, pentafluoro, 2-methyl-4-fluoro, 2-trifluoromethyl, 2-methoxy-6-fluoro, 2-chloro, 2 Fluorine, 2,4-difluoro, 2-fluoro-4-chloro, 2-chloro-4-fluoro, 2-chloro-5-fluoro, 2,3-difluoro, 2,5-difluoro, 2,3,4 Trifluoro, 2-methyl, 2,4-dimethyl, 2-methyl-4-chloro, 2-methyl-5-fluoro, 2-fluoro-4-methyl, 2,6-dimethyl, 2,4,6-trimethyl , 2,6-Difluoro-4-methyl, 2-trifluoromethyl-4-fluoro, 2-trifluoromethyl-5-fluoro or 2-trifluoromethyl-5-chloro.

In In one embodiment, the index m is zero.

In In another embodiment, the index m has the value 1.

In In another embodiment, the index m has the value 2.

In one embodiment of the compounds IB, R ^{3 is} pyridine, pyrimidine, pyridazine or pyrazine.

One embodiment relates to compounds IB, in which R ^{3 is} pyridyl which is linked in the 2-, 3- or 4-position and may be monosubstituted, monosubstituted or differently substituted by L _m , which is preferably fluorine, chlorine, bromine , Cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl. Embodiments of the compounds of the formula I relate to those of the formula I.B1 and I.B2.

A further embodiment relates to compounds IB in which R ^{3 is} pyrimidyl which is linked in the 4- or 5-position and may be monosubstituted or disubstituted by identical or different substituents by L _m , which preferably comprises fluorine, chlorine, bromine, cyano , Nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl. Embodiments of the compounds of the formula I relate to those of the formula I.B3 and I.B4.

Another embodiment relates to compounds IB in which R ^{3 is} thienyl, which is in the 2- or 3-part ment and may be monosubstituted or disubstituted by L _m which is preferably fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl means. Embodiments of the compounds of the formula I relate to those of the formula I.B5, I.B6 and I.B7.

A further embodiment relates to compounds IB in which R ^{3 is} thiazolyl which is linked in the 2-, 4- or 5-position and may be substituted by L _m , which preferably comprises fluorine, chlorine, bromine, cyano, nitro, methyl , Ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl or trifluoromethyl. One embodiment of the compounds of the formula I relates to those of the formula I.B8.

Another embodiment relates to compounds IB in which R ^{3 is} imidazolyl which is linked in the 4- or 5-position and may be monosubstituted or disubstituted by identical or different substituents by L _m , which preferably comprises fluorine, chlorine, bromine, cyano , Nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl. Embodiments of the compounds of the formula I relate to those of the formula I.B9 and I.B10.

A further embodiment relates to compounds IB in which R ^{3 is} pyrazolyl which is linked in the 1-, 3-, 4- or 5-position and may be monosubstituted to trisubstituted, identically or differently substituted by L _m , which is preferably fluorine , Chloro, bromo, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl. Embodiments of the compounds of the formula I relate to those of the formula I.B11, I.B12 and I.B13.

A further embodiment relates to compounds IB in which W is oxazolyl which is linked in the 2-, 4- or 5-position and may be monosubstituted or disubstituted by identical or different substituents by L _m , which is preferably fluorine, chlorine, bromine , Cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximino ethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl. Embodiments of the compounds of the formula I relate to those of the formula I.B14 and I.B15.

The index m, if structurally possible, is preferably from 1 to 3, where the groups L may be identical or different. If the heteroaromatic groups R ^{3 in} addition to a group L ¹ carry further substituents L _m , these are preferably selected from: fluorine, chlorine, methyl, methoxy, cyano, nitro, alkoxycarbonyl and haloalkyl. In a further embodiment, the optional substituents L _{m are} selected from fluorine, chlorine, methyl and methoxy. In a further embodiment, the optional substituents L _{m are} selected from chlorine, methyl and methoxy.

In one embodiment of compounds 1.0, R ^{3 is} pyrazol-1-yl.

One embodiment relates to compounds 1.0, in which R ^{3 is} pyrazol-1-yl, which may be monosubstituted to trisubstituted by identical or different substituents in the 3-, 4- or 5-position by L _m , which is preferably chlorine, bromine and / or methyl. Embodiments of the compounds of the formula I relate to those of the formula I.C1 and I.C2.

Especially are in terms of their use in the following tables Compounds I are preferred. The in the tables In addition, groups named for a substituent represent individually, regardless of the combination, in which they are called, a particularly preferred embodiment of the relevant substituent.

Table 1

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-6-chlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 2

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-difluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 3

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-dichlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 4

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-6-methylphenyl and R ² for each compound corresponds to one row of Table A.

Table 5

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4,6-trifluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 6

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-difluoro-4-methoxyphenyl and R ² for each compound corresponds to one row of Table A.

Table 7

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-4-methoxyphenyl and R ² for each compound corresponds to one row of Table A.

Table 8

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pentafluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 9

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-4-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 10

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-trifluoromethylphenyl and R ² for each compound corresponds to one row of Table A.

Table 11

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methoxy-o-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 12

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 13

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 14

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-difluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 15

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-4-chlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 16

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-4-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 17

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-5-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 18

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,3-difluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 19

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-difluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 20

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,3,4-trifluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 21

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methylphenyl and R ² for each compound corresponds to one row of Table A.

Table 22

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-dimethylphenyl and R ² for each compound corresponds to one row of Table A.

Table 23

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-4-chlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 24

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 25

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-4-methylphenyl and R ² for each compound corresponds to one row of Table A.

Table 26

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-dimethylphenyl and R ² for each compound corresponds to one row of Table A.

Table 27

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4,6-trimethylphenyl and R ² for each compound corresponds to one row of Table A.

Table 28

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-difluoro-4-methylphenyl and R ² for each compound corresponds to one row of Table A.

Table 29

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-trifluoromethyl-4-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 30

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-trifluoromethyl-5-fluorophenyl and R ² for each compound corresponds to one row of Table A.

Table 31

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-trifluoromethyl-5-chlorophenyl and R ² for each compound corresponds to one row of Table A.

Table 32

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-pyridinyl and R ² for each compound corresponds to one row of Table A.

Table 33

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-cyanopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 34

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 35

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 36

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 37

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-ethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 38

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 6-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 39

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-trifluoromethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 40

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-trifluoromethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 41

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-fluoropyridin-2-yl and R ² for a compound corresponds in each case to one row of Table A.

Table 42

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 43

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-difluoropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 44

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dichloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 45

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 46

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 47

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyrazine-2-yl and R ² for each compound corresponds to one row of Table A.

Table 48

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyridazin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 49

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 6-chloropyridazin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 50

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,3,5-triazin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 51

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 52

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 53

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} pyrimidin-5-yl and R ² for each compound corresponds to one row of Table A.

Table 54

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-6-trifluoromethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 55

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dimethyl-6-trifluoromethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 56

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 6-trifluoromethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 57

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-methyl-6-trifluoromethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 58

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-chloro-6-methylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 59

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-bromo-6-methylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 60

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-fluoro-6-methylpyrimidin-4-yl and R ² for a compound corresponds in each case to one row of Table A.

Table 61

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-chloropyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 62

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-fluoropyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 63

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-bromopyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 64

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-fluoropyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 65

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-chloropyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 66

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-bromopyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 67

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-dimethyl-5-chloropyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 68

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,6-dimethyl-5-bromopyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 69

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-fluoro-6-fluoromethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 70

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5,6-dimethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 71

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dimethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 72

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5,6-trimethylpyrimidin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 73

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dimethylpyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 74

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,5,6-trimethylpyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 75

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-di (trifluoromethyl) pyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 76

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dimethyl-5-chloropyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 77

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dimethyl-5-bromopyrimidin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 78

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methylpyrimidin-5-yl and R ² for each compound corresponds to one row of Table A.

Table 79

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dimethylpyrimidin-5-yl and R ² for each compound corresponds to one row of Table A.

Table 80

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-trifluoromethyl-6-methylpyrimidin-5-yl and R ² for each compound corresponds to one row of Table A.

Table 81

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4,6-trimethylpyrimidin-5-yl and R ² for each compound corresponds to one row of Table A.

Table 82

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 83

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-bromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 84

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-nitropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 85

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-chloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 86

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-bromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 87

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-ethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 88

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-chloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 89

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-bromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 90

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 91

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-ethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 92

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-cyanopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 93

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-fluoropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 94

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-bromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 95

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 96

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-ethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 97

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-cyanopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 98

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-fluoropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 99

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-chloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 100

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-bromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 101

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dimethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 102

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-ethylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 103

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-cyanopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 104

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-bromo-5-fluoropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 105

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-bromo-5-chloropyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 106

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-bromo-5-methylpyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 107

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dibromopyridin-2-yl and R ² for each compound corresponds to one row of Table A.

Table 108

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoropyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 109

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloropyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 110

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-bromopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 111

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 112

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-difluoropyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 113

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-chloropyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 114

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-bromopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 115

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-methylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 116

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-ethylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 117

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-fluoro-5-cyanopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 118

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dichloro-5-chloropyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 119

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-bromopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 120

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-methylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 121

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-ethylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 122

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloro-5-cyanopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 123

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dimethylpyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 124

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-bromopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 125

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-cyanopyridin-4-yl and R ² for each compound corresponds to one row of Table A.

Table 126

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 127

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 128

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 129

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 130

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 131

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 132

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 133

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 134

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-difluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 135

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-4-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 136

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-4-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 137

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-fluoro-4-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 138

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-dichloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 139

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-4-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 140

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-4-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 141

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-chloro-4-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 142

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-dimethylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 143

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-4-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 144

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-4-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 145

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-bromo-4-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 146

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-bromo-4-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 147

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-bromo-4-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 148

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-difluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 149

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoro-6-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 150

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoro-6-bromopyridin-3-yl and R ² for a compound corresponds in each case to one row of Table A.

Table 151

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoro-6-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 152

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoro-6-ethylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 153

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-fluoro-6-cyanopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 154

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dichloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 155

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 156

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 157

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 158

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-ethylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 159

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-methoxypyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 160

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-cyanopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 161

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-cyanopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 162

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-6-nitropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 163

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methyl-6-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 164

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methyl-6-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 165

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methyl-6-bromopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 166

Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,6-dimethylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 167

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methyl-6-cyanopyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 168

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-bromo-6-fluoropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 169

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-bromo-6-chloropyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 170

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-bromo-6-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 171

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,4-dichloro-6-methylpyridin-3-yl and R ² for each compound corresponds to one row of Table A.

Table 172

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,3-dimethylpyrazol-5-yl and R ² for each compound corresponds to one row of Table A.

Table 173

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1-methyl-3-trifluoromethylpyrazol-5-yl and R ² for each compound corresponds to one row of Table A.

Table 174

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,5-dimethylpyrazol-3-yl and R ² for each compound corresponds to one row of Table A.

Table 175

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,3,5-trimethylpyrazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 176

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1-methyl-3-trifluoromethylpyrazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 177

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,3-dimethylpyrazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 178

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1-methyl-5-trifluoromethylpyrazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 179

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1,5-dimethylpyrazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 180

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methylthiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 181

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} thiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 182

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-chlorothiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 183

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dichlorothiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 184

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyl-5-bromothiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 185

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methylisothiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 186

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methyl-5-chloroisothiazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 187

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ³ isoxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 188

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dimethylisoxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 189

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-chloroisoxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 190

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methylisoxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 191

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} oxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 192

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dimethyloxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 193

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methyloxazol-4-yl and R ² for each compound corresponds to one row of Table A.

Table 194

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-thienyl and R ² for each compound corresponds to one row of Table A.

Table 195

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dichlorothiophen-2-yl and R ² for each compound corresponds to one row of Table A.

Table 196

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,4,5-trichlorothiophen-2-yl and R ² for each compound corresponds to one row of Table A.

Table 197

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-chlorothio-phen-2-yl and R ² for each compound corresponds to one row of Table A.

Table 198

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-bromothiophen-2-yl and R ² for each compound corresponds to one row of Table A.

Table 199

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-methylthiophen-2-yl and R ² for each compound corresponds to one row of Table A.

Table 200

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dichlorothiophen-3-yl and R ² for each compound corresponds to one row of Table A.

Table 201

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2,5-dibromothiophene-3-yl and R ² for each compound corresponds to one row of Table A.

Table 202

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 2-methylthiophen-3-yl and R ² for each compound corresponds to one row of Table A.

Table 203

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 1-methyl-5-methoxypyrazol-3-yl and R ² for each compound corresponds to one row of Table A.

Table 204

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3-methylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 205

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-methylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 206

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 5-methylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 207

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,4-dimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 208

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4,5-dimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 209

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,5-dimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 210

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 3,4,5-trimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 211

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-chloro-3,5-dimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table 212

• Compounds of the formula I in which R ¹ and R ^{4 are} each chlorine and R ^{3 is} 4-bromo-3,5-dimethylpyrazol-1-yl and R ² for each compound corresponds to one row of Table A.

Table A

In addition to the compounds individualized in Tables 1 to 212, the corresponding derivatives in which R ¹ and R ^{4 are} cyano are further objects of the invention.

In addition to the compounds individualized in Tables 1 to 212, the corresponding derivatives in which R ¹ and R ^{4 are} methoxy are further objects of the invention.

The Compounds I are useful as fungicides. They are distinguished by an excellent effectiveness against a broad spectrum phytopathogenic fungi of the Ascomycetes class, Deuteromycetes, Basidiomycetes and Peronosporomycetes (syn. Oomycetes). you are sometimes systemically effective and can be used in crop protection be used as foliar, pickling and soil fungicides.

Special They have meaning for fighting a variety of mushrooms on various crops such as wheat, rye, barley, Oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, Wine, fruit and ornamental plants and vegetables such as cucumbers, Beans, tomatoes, potatoes and pumpkins, as well as on the Seeds of these plants. You can also work in cultures that through breeding, including genetic engineering Methods that are tolerant to insect or fungal attack are used become. In addition, they are suitable for the Combat Botrytis osphaeria species, Cylindrocarpon species, Eutypa lata, Neonectria liriodendri and Stereum hirsutum, under the vine or the roots of grapevines.

In particular, they are suitable for controlling the following plant diseases:
Alternaria species on vegetables, oilseed rape, sugarbeet, fruit, rice, soybeans and on potatoes (eg BA solani or A. alternata) and tomatoes (eg BA solani or A. alternata) and Alternaria ssp. (Spikelet) on wheat,
Aphanomyces species of sugar beets and vegetables,
Ascochyta species on cereals and vegetables z. B. Ascochyta tritici (leaf drought) on wheat,
Bipolaris and Drechslers types of maize (eg BD maydis), cereals, rice and turf,
Blumeria graminis (powdery mildew) on cereals (eg wheat or barley),
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers, vines and wheat (spike mold),
Bremia lactucae on salad,
Cercospora species on corn, rice, sugar beets and z. B. Cercospora sojina (leaf spot) or Cercospora kikuchii (leaf spot) on soybeans,
Cladosporium herbarum (earwars) on wheat,
Cochliobolus species on corn, cereals (eg Cochliobolus sativus) and rice (eg Cochliobolus miyabeanus),
Colletotricum species on cotton and z. B. Colletotrichum truncatum (Antracnose) on soybeans
Corynespora cassiicola (leaf spot) on soybeans,
Dematophora necatrix (root / stem rot) on soybeans,
Diaporthe phaseolorum (stalk disease) on soybeans,
Drechslers species, Pyrenophora species on corn, cereals, rice and turf, barley (eg BD teres) and wheat (eg BD tritici-repentis),
Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),
Elsinoe ampelina on grapevine,
Epicoccum spp. (Spikelet) on wheat,
Exserohilum species on corn,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Fusarium and Verticillium species on different plants: e.g. BF graminearum or F. culmorum (root rot) on cereals (eg wheat or barley) or z. BF oxysporum on tomatoes and Fusarium solani (stalk disease) on soybeans
Gaeumanomyces graminis (root black) on cereals (eg wheat or barley),
Gibberella species on cereals and rice (eg Gibberella fujikuroi),
Glomerella cingulata on grapevine and other plants,
Grainstaining complex on rice,
Guignardia budwelli on grapevine,
Helminthosporium species on corn and rice,
Isariopsis clavispora on grapevine,
Macrophomina phaseolina (root / stem rot) on soybeans,
Michrodochium nivale (snow mold) on cereals (eg wheat or barley),
Microsphaera diffusa (powdery mildew) on soybeans,
Mycosphaerella species on cereals, bananas and peanuts, such as. BM graminicola on wheat or M. fijiensis on bananas,
Peronospora species on cabbage (for example BP brassicae), bulbous plants (for example BP destructor) and z. B. Peronospora manshurica (downy mildew) on soybeans
Phakopsara pachyrhizi (soybean rust) and Phakopsara meibomiae (soybean rust) on soybeans,
Phialophora gregata (stalk disease) on soybeans
Phomopsis species on sunflowers, grapevine (eg BP viticola) and soybeans (eg Phomopsis phaseoli),
Phytophthora species on various plants z. BP capsici on peppers, Phytopthora megasperma (leaf / stem rot) on soybeans, Phytophthora infestans on potatoes and tomatoes,
Plasmopara viticola on vines,
Podosphaera leucotricha on apple,
Pseudocercosporella herpotrichoides (crushed straw) on cereals (wheat or barley),
Pseudoperonospora on various plants z. BP cubensis on cucumber or P. humili on hops,
Pseudo-pedicel tracheiphilai on grapevine,
Puccinia species on different plants z. BP triticina, P. striformins, P. hordei or P. graminis on cereals (eg wheat or barley) or on asparagus (eg BP asparagi),
Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum,
Pyrenophora tritici-repentis (leaf drought) on wheat or Pyrenophora teres (net spots) on barley,
Entyloma oryzae on rice,
Pyricularia grisea on lawn and cereals,
Pythium spp. on grass, rice, maize, wheat, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants (eg BP ultiumum or P. aphanidermatum),
Ramularia collo-cygni (Ramularia / sunburn complex / Physiological leaf spots) on barley,
Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants such. B. Rhizoctonia solani (root / stem rot) on soybeans or Rhizoctonia cerealis (Spitzer Augenfleck) on wheat or barley,
Rhynchosporium secalis on barley, rye and triticale,
Sclerotinia species on oilseed rape, sunflowers and z. Sclerotinia sclerotiorum (stalk disease) or Sclerotinia rolfsii (stalk disease) on soybeans,
Septoria glycines (leaf spots) on soybeans,
Septoria tritici (leaf septoria) and Stagonospora nodorum on wheat,
Erysiphe (Syn. Uncinula) necator on grapevine,
Setospaeria species on corn and turf,
Sphacelotheca reilinia on corn,
Stagonospora nodorum (ear septoria) on wheat,
Thievaliopsis species on soybeans and cotton,
Tilletia species of cereals,
Typhula incarnata (snow) on wheat or barley,
Ustilago species on cereals, corn (such as maydis) and sugar cane,
Venturia species (scab) on apples (eg BV inaequalis) and pears.

The Compounds I are also suitable for controlling of harmful fungi in the protection of materials (eg wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products. In wood preservation, the following harmful fungi in particular are considered: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus Spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.

The Compounds I are applied by adding the mushrooms or the pre Fungus to protect plants, seeds, Materials or the soil with a fungicidally effective amount treated the active ingredients. The application can be both before and after infection of the materials, plants or seeds by the Mushrooms done.

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

The Application rates depending on the application in crop protection Type of effect desired between 0.01 and 2.0 kg of active ingredient per ha.

at Seed treatment are generally drug quantities of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed needed.

at the application in material or storage protection, the application rate depends on active ingredient according to the type of application and the desired Effect. Usual application rates are in material protection, for example 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter treated material.

The Compounds of formula I may be in various crystal modifications present, which differ in their biological effectiveness can. They are also subject of the present Invention.

The Compounds I can be converted into the customary formulations be, for. Solutions, emulsions, suspensions, dusts, Powders, pastes and granules. The application form depends on the respective purpose; she should be fine in any case and uniform distribution of the invention Ensure connection.

• – Wasser, aromatische Lösungsmittel (z. B. Solvesso^® Produkte, Xylol), Paraffine (z. B. Erdölfraktionen), Alkohole (z. B. Methanol, Butanol, Pentanol, Benzylalkohol), Ketone (z. B. Cyclohexanon, gamma-Butryolacton), Pyrrolidone (NMP, NOP), Acetate (Glykoldiacetat), Glykole, Dimethylfettsäureamide, Fettsäuren und Fettsäureester. Grundsätzlich können auch Lösungsmittelgemische verwendet werden.
• – Trägerstoffe wie natürliche Gesteinsmehle (z. B. Kaoline, Tonerden, Talkum, Kreide) oder synthetische Gesteinsmehle (z. B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z. B. Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin-Sulfitablaugen und Methylcellulose.

The formulations are prepared in a known manner, for. B. by stretching the active compounds with solvents and carriers or solvents or carriers, if desired using other auxiliaries such as emulsifiers or dispersants. Individual substances can also fulfill different functions. Suitable solvents, carriers or auxiliaries are essentially:

• - water, aromatic solvents (. For example Solvesso ^® products, xylene), paraffins (for., For example petroleum fractions), alcohols, ketones (for example cyclohexanone, gamma (e.g., methanol, butanol, pentanol, benzyl alcohol.). Butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used.
• - Carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) or ground synthetic minerals (eg highly disperse silicic acid, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

The compositions of the invention may be formulated in solid form or in liquid form. Depending on the embodiment, the compositions according to the invention may also contain auxiliaries and / or Contain carriers such as are customary in crop protection agents or in materials for protection of materials. The auxiliaries include, in particular, conventional surface-active substances and other additives customary in plant and material protection and carriers which may be solid or liquid. The surface-active substances include, in particular, surfactants, in particular those which have wetting agent properties. The other auxiliaries (additives) include, in particular, thickeners, defoamers, preservatives, antifreeze agents, stabilizers, anticaking agents or flow aids and buffers.

in principle useful conventional surfactants are anionic, nonionic and amphoteric surfactants, including Polymer surfactants, wherein the molecular weight of the surfactants typically do not exceed a value of 2000 daltons and in particular 1000 daltons becomes (number average).

To the anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, z. As potassium stearate, which is commonly used as soaps be designated; glutamates; Sarcosinates, e.g. For example, sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, in particular mono- and Diphosphorsäurealkylester; Sulfates, in particular alkyl sulfates and alkyl ether sulfates; Sulfonates, other alkyl and alkylaryl sulfonates, in particular alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acid, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, Alkylnaphthalenesulfonates, alkylmethyl ester sulfonates, condensation products sulfonated naphthalene and derivatives thereof with formaldehyde, Condensation products of naphthalenesulfonic acids, phenolic and / or phenolsulfonic acids with formaldehyde or with formaldehyde and Urea, mono- or dialkylsuccinic acid sulfonates; as well as protein hydrolysates and lignin-sulphite waste liquors. The The aforementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.

• – Fettalkoholalkoxylate und Oxoalkoholalkoxylate, insbesondere Ethoxylate und Propoxylate mit Alkoxilierungsgraden von üblicherweise 2 bis 100 und insbesondere 3 bis 50, z. B. Alkoxylate von C₈-C₃₀-Alkanolen oder Alk(adi)enolen, z. B. von iso-Tridecylalkohol, Laurylalkohol, Oleylalkohol oder Stearylalkohol sowie deren C₁-C₄-Alkylether und C₁-C₄-Alkylester z. B. deren Acetate;
• – alkoxylierte tierische und/oder pflanzliche Fette und/oder Öle, beispielsweise Maisölethoxylate, Rizinusölethoxylate, Talgfettethoxylate,
• – Glycerinester, wie beispielsweise Glycerinmonostearat,
• – Alkylphenolalkoxylate, wie beispielsweise ethoxyliertes iso-Octyl-, Octyl- oder Nonylphenol, Tributylphenolpolyoxyethylenether,
• – Fettaminalkoxylate, Fettsäureamid- und Fettsäurediethanolamidalkoxylate, insbesondere deren Ethoxylate,
• – Zuckertenside, Sorbitester, wie beispielsweise Sorbitanfettsäureester (Sorbitanmonooleat, Sorbitantristearat), Polyoxyethylensorbitanfettsäureester, Alkylpolyglycoside, N-Alkylgluconamide,
• – Alkylmethylsulfoxide,
• – Alkyldimethylphosphinoxide, wie beispielsweise Tetradecyldimethylphosphinoxid.

Nonionic surfactants include, for example:

• Fatty alcohol alkoxylates and oxo alcohol alkoxylates, in particular ethoxylates and propoxylates having degrees of alkoxylation of usually 2 to 100 and in particular 3 to 50, eg. B. alkoxylates of C ₈ -C ₃₀ alkanols or alk (adi) enols, z. Example of iso-tridecyl alcohol, lauryl alcohol, oleyl alcohol or stearyl alcohol and their C ₁ -C ₄ alkyl ethers and C ₁ -C ₄ alkyl esters z. B. their acetates;
• Alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates,
• Glycerol esters, such as glycerol monostearate,
• Alkyl phenol alkoxylates, such as, for example, ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,
• Fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, in particular their ethoxylates,
• Sugar surfactants, sorbitol esters such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkylpolyglycosides, N-alkylgluconamides,
• - alkylmethyl sulfoxides,
• - Alkyldimethylphosphinoxide, such as Tetradecyldimethylphosphinoxid.

To The amphoteric surfactants include, for example, sulfobetaines, Carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide.

Further Surfactants to be exemplified here are perfluorosurfactants, Silicone surfactants, phospholipids, such as lecithin or chemically modified lecithins, amino acid surfactants, e.g. B. N-lauroylglutamate.

to Production of directly sprayable solutions, Emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and vegetable or vegetable oils animal origin, aliphatic, cyclic and aromatic hydrocarbons, z. For example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated Naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, Cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, z. As dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powder-, Spreading and dusting can be done by mixing or co-grinding the active components A and B and, as far as present, further active ingredients prepared with at least one solid carrier become.

Granules, for. B. wrapping, impregnating and homogeneous granules can by binding the Active ingredients are prepared on at least one solid carrier. Solid carriers are z. As mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The Formulations of the compounds of the invention generally contain from 0.01 to 95 wt .-%, preferably 0.1 to 90 wt .-% of the compounds I and II. The active ingredients are thereby preferably in a purity of 90% to 100%, preferably 95% to 100% used.

For Seed treatment yields the relevant formulations two to tenfold dilution drug concentrations from 0.01 to 60 wt .-%, preferably 0.1 to 40 wt .-% in the finished usable preparations.

The Formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are in a purity of 90% to 100%, preferably 95% up to 100% (according to NMR spectrum) used.

Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 Parts by weight of the active ingredients are mixed with 90 parts by weight of water or dissolved in a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% Drug content.

B Dispersible Concentrates (DC)

20 Parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant z. For example, polyvinylpyrrolidone solved. Dilution in water results in a Dispersion. The active ingredient content is 20% by weight

C Emulsifiable Concentrates (EC)

15 Parts by weight of the active ingredients are added in 75 parts by weight of xylene with addition of Ca-dodecylbenzenesulfonate and castor oil ethoxylate (each 5 parts by weight) dissolved. When diluting in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 Parts by weight of the active ingredients are added in 35 parts by weight of xylene with addition of Ca-dodecylbenzenesulfonate and castor oil ethoxylate (each 5 parts by weight) dissolved. This mixture is made by means of a Emulsifying machine (eg Ultraturax) in 30 parts by weight of water and brought to a homogeneous emulsion. When diluting in water results in an emulsion. The wording has one Active ingredient content of 25 wt .-%.

E suspensions (SC, OD, FS)

20 Parts by weight of the active compounds are added with the addition of 10 parts by weight Dispersing and wetting agents and 70 parts by weight of water or a organic solvent in a stirred ball mill crushed to a fine suspension of active ingredient. When diluting in water results in a stable suspension of the active ingredient. Of the Active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble Granules (WG, SG)

50 Parts by weight of the active ingredients are added with the addition of 50 parts by weight Dispersing and wetting agents finely ground and by means of technical Equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active substance content of 50% by weight.

G Water-dispersible and water-soluble Powder (WP, SP, SS, WS)

75 Parts by weight of the active ingredients are added with the addition of 25 parts by weight Dispersing and wetting agents and silica gel in one Milling the rotor-strator mill. When diluting in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations (GF)

In a ball mill are 20 parts by weight of the active ingredients, 10 Parts by weight of dispersant, 1 part by weight of swelling agent ("gelling Agent ") and 70 parts by weight of water or an organic solvent milled to a fine suspension. When diluting With water results in a stable suspension with 20 wt .-% active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 Parts by weight of the active ingredients are ground finely and with 95 parts by weight finely divided kaolin intimately mixed. You get it a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 Gew parts of the active ingredients are finely ground and with 99.5 parts by weight Carriers connected. Common methods are while the extrusion, the spray-drying or the fluidized bed. This gives granules for direct application with 0.5% by weight active ingredient content.

K ULV solutions (UL)

10 Parts by weight of the active compounds are dissolved in 90 parts by weight of an organic Solvent z. B. dissolved xylene. This preserves one product for direct application with 10% by weight Drug content.

For Seed treatment usually become water-soluble Concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) used. These formulations may be undiluted on the seed or, preferably, be applied diluted. The application may be before Sowing done.

The Active substances can, as such, in the form of their formulations or the use forms prepared from it, eg. B. in the form of direct sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, Dusts, scattering agents, granules by spraying, Misting, dusting, scattering or pouring be applied. The forms of application depend entirely on the intended use; In any case they should be as fine as possible to ensure the active compounds of the invention.

aqueous Application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) Addition of water to be prepared. For the preparation of emulsions, pastes or oil dispersions may be the substances as such or dissolved in an oil or solvent, by means of Wetting, adhesive, dispersing or emulsifying agent homogenized in water become. But it can also be made of effective substance network, Adhesive, dispersing or emulsifying agents and possibly solvents or oil existing concentrates are produced, the suitable for dilution with water.

The Active substance concentrations in the ready-to-use preparations can be varied in larger areas become. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The Active ingredients can also be successfully used in ultra-low-volume procedures (ULV), it being possible to use formulations with more than 95 wt .-% active ingredient or even the active ingredient without additives deploy.

The active substances may include oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also immediately before use (Tank mix), to be added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

Suitable adjuvants in this sense are in particular: organically modified polysiloxanes, for. B. Break Thru S ^240® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluronic RPE 2035 ^® and Genapo) B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e.g. B. Leophen RA ^®.

The agents according to the invention can be used in the Form of application as fungicides also together with other active ingredients present, the z. With herbicides, insecticides, growth regulators, Fungicides or even with fertilizers. When mixing the compounds (I) or the agents containing them with a or several other active ingredients, in particular fungicides For example, in many cases broadened the spectrum of action or resistance developments are prevented. In many Cases are obtained thereby synergistic effects. The fungicides are preferably selected from the following Groups. Preferred representatives from these groups are in the table Called B

strobilurins, Carboxylic acid amides such as carboxylic acid anilides, carboxylic acid morpholides, Benzoic acid amides, other carboxylic acid amides, azoles such as triazoles, imidazoles, benzimidazoles, others, nitrogenous Heterocyclyl compounds such as pyridines, pyrimidines, pyrroles, morpholines, Dicarboximides, other nitrogen-containing heterocyclyl compounds, Thio- and dithiocarbamates, carbamates, guanidines, antibiotics, nitrophenyl derivatives, Organometallic compounds, Sulfur-containing heterocyclyl compounds, Organophosphorus compounds, organochlorine compounds, inorganic Active ingredients, other fungicides.

Accordingly, the present invention further relates to the compositions listed in Table B, wherein in each case one row of Table B corresponds to a fungicidal composition comprising a compound of the formula I (component 1), which is preferably one of the compounds described herein as preferred, and the in each case indicated in the relevant line further active ingredient (component 2). According to one embodiment of the invention, component 1 in each row of Table B is in each case one of the compounds of the formula I which are specifically individualized in Tables 1 to 212 row Component 1 Component 2 B-1 a compound of formula I azoxystrobin B-2 a compound of formula I dimoxystrobin B-3 a compound of formula I enestroburin B-4 a compound of formula I fluoxastrobin B-5 a compound of formula I Kresoxim-methyl B-6 a compound of formula I metominostrobin B-7 a compound of formula I orysastrobin B-8 a compound of formula I picoxystrobin B-9 a compound of formula I pyraclostrobin B-10 a compound of formula I pyribencarb B-11 a compound of formula I trifloxystrobin B-12 a compound of formula I 2- (2- (6- (3-chloro-2-methyl-phenoxy) -5-fluoro-pyrimidin-4-yloxy) -phenyl) -2-methoxyimino-N-methylacetamide B-13 a compound of formula I 2- (ortho - ((2,5-dimethylphenyl-oxymethylene) phenyl) -3-methoxy-methyl acrylate B-14 a compound of formula I 3-methoxy-2- (2- (N- (4-methoxy-phenyl) -cyclopropancarboximidoylsulfanylmethyl) phenyl) -acrylic acid methyl ester B-15 a compound of formula I benalaxyl B-16 a compound of formula I Benalaxyl-M B-17 a compound of formula I Benodanil B-18 a compound of formula I bixafen B-19 a compound of formula I boscalid B-20 a compound of formula I carboxin B-21 a compound of formula I fenfuram B-22 a compound of formula I fenhexamid B-23 a compound of formula I flutolanil B-24 a compound of formula I furametpyr B-25 a compound of formula I isotianil B-26 a compound of formula I Kiralaxyl B-27 a compound of formula I mepronil B-28 a compound of formula I metalaxyl B-29 a compound of formula I ofurace B-30 a compound of formula I oxadixyl B-31 a compound of formula I oxycarboxin B-32 a compound of formula I penthiopyrad B-33 a compound of formula I Thifluzamide B-34 a compound of formula I tecloftalam B-35 a compound of formula I tiadinil B-36 a compound of formula I 2-amino-4-methyl-thiazol-5-carboxanilide B-37 a compound of formula I 2-chloro-N- (1,1,3-trimethyl-indan-4-yl) -nicotinamide B-38 a compound of formula I N- (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-39 a compound of formula I 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2- (1,3-dimethyl-butyl) -phenyl] -amide B-40 a compound of formula I N- (4'-chloro-3 ', 5-difluoro-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-41 a compound of formula I N- (4'-chloro-3 ', 5-difluoro-biphenyl-2-yl) -3-tri-fluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-42 a compound of formula I N- (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) -3-tri-fluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-43 a compound of formula I N- (3 ', 5-difluoro-4'-methyl-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-44 a compound of formula I N- (3 ', 5-difluoro-4'-methyl-biphenyl-2-yl) -3-tifluormethyl-i-methyl-IH-pyrazole-4-carboxamide B-45 a compound of formula I N- (2-bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-46 a compound of formula I N- (cis-2-bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-47 a compound of formula I N- (trans-2-bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-48 a compound of formula I dimethomorph B-49 a compound of formula I flumorph B-50 a compound of formula I flumetover B-51 a compound of formula I Fluopicolide (picobenzamide) B-52 a compound of formula I fluopyram B-53 a compound of formula I zoxamide B-54 a compound of formula I N- (3-ethyl-3,5-5trimethyl-cyclohexyl) -3-formylamino-2-hydroxy-benzamide B-55 a compound of formula I carpropamid B-56 a compound of formula I diclocymet B-57 a compound of formula I mandipropamid B-58 a compound of formula I oxytetracycline B-59 a compound of formula I silthiofam B-60 a compound of formula I N- (6-methoxy-pyridin-3-yl) cyclopropane-carboxamide B-61 a compound of formula I azaconazole B-62 a compound of formula I bitertanol B-63 a compound of formula I bromuconazole B-64 a compound of formula I cyproconazole B-65 a compound of formula I Difenoconazole B-66 a compound of formula I diniconazole B-67 a compound of formula I Diniconazole-M B-68 a compound of formula I Enilconazole B-69 a compound of formula I epoxiconazole B-70 a compound of formula I Fenbuconazole B-71 a compound of formula I flusilazole B-72 a compound of formula I fluquinconazole B-73 a compound of formula I flutriafol B-74 a compound of formula I hexaconazole B-75 a compound of formula I Imibenconazole B-76 a compound of formula I ipconazole B-77 a compound of formula I metconazole B-78 a compound of formula I myclobutanil B-79 a compound of formula I oxpoconazole B-80 a compound of formula I paclobutrazol B-81 a compound of formula I penconazole B-82 a compound of formula I propiconazole B-83 a compound of formula I prothioconazole B-84 a compound of formula I Simeconazole B-85 a compound of formula I tebuconazole B-86 a compound of formula I tetraconazole B-87 a compound of formula I triadimenol B-88 a compound of formula I triadimefon B-89 a compound of formula I triticonazole B-90 a compound of formula I uniconazole B-91 a compound of formula I 1- (4-chloro-phenyl) -2 - ([1,2,4] triazol-1-yl) cycloheptanol B-92 a compound of formula I cyazofamid B-93 a compound of formula I imazalil B-94 a compound of formula I Imazalil sulphate B-95 a compound of formula I Pefurazoate B-96 a compound of formula I prochloraz B-97 a compound of formula I triflumizole B-98 a compound of formula I benomyl B-99 a compound of formula I carbendazim B-100 a compound of formula I fuberidazole B-101 a compound of formula I thiabendazole B-102 a compound of formula I ethaboxam B-103 a compound of formula I etridiazole B-104 a compound of formula I hymexazole B-105 a compound of formula I fluazinam B-106 a compound of formula I pyrifenox B-107 a compound of formula I 1- (4-chloro-phenyl) -1- (propyn-2-yloxy) -3- (4- (3,4-dimethoxy-phenyl) -isoxazole-5-yl) -propan-2-one B-108 a compound of formula I 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine B-109 a compound of formula I 2,3,5,6-tetrachloro-4-methanesulfonylpyridine B-110 a compound of formula I 3,4,5-trichloro-pyridine-2,6-dicarbonitrile B-111 a compound of formula I N- (1- (5-bromo-3-chloro-pyridin-2-yl) ethyl) -2,4-dichloro-nicotinamide B-112 a compound of formula I N - ((5-bromo-3-chloro-pyridin-2-yl) methyl) -2,4-dichloro-nicotinamide B-113 a compound of formula I Bupirimate B-114 a compound of formula I cyprodinil B-115 a compound of formula I diflumetorim B-116 a compound of formula I Ferimzone B-117 a compound of formula I fenarimol B-118 a compound of formula I mepanipyrim B-119 a compound of formula I nitrapyrin B-120 a compound of formula I nuarimol B-121 a compound of formula I pyrimethanil B-122 a compound of formula I fludioxonil 6-123 a compound of formula I fenpiclonil B-124 a compound of formula I aldimorph B-125 a compound of formula I dodemorph B-126 a compound of formula I Dodemorph acetate B-127 a compound of formula I fenpropimorph B-128 a compound of formula I tridemorph B-129 a compound of formula I Fluoroimid B-130 a compound of formula I iprodione B-131 a compound of formula I procymidone B-132 a compound of formula I vinclozolin B-133 a compound of formula I Acibenzolar-S-methyl B-134 a compound of formula I amisulbrom B-135 a compound of formula I anilazine B-136 a compound of formula I Blasticidin S B-137 a compound of formula I captan B-138 a compound of formula I captafol B-139 a compound of formula I chinomethionat B-140 a compound of formula I dazomet B-141 a compound of formula I debacarb B-142 a compound of formula I Diclomezine B-143 a compound of formula I difenzoquat B-144 a compound of formula I Difenzoquat methylsulphat B-145 a compound of formula I famoxadone B-146 a compound of formula I fenamidone B-147 a compound of formula I fenoxanil B-148 a compound of formula I fenpropidin B-149 a compound of formula I folpet B-150 a compound of formula I Octhilinone B-151 a compound of formula I oxolinic B-152 a compound of formula I piperalin B-153 a compound of formula I Probenazole B-154 a compound of formula I proquinazid B-155 a compound of formula I pyroquilon B-156 a compound of formula I quinoxyfen B-157 a compound of formula I triazoxide B-158 a compound of formula I Tricyclazole B-159 a compound of formula I triforine B-160 a compound of formula I 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine B-161 a compound of formula I 2-butoxy-6-iodo-3-propyl-chromen-4-one B-162 a compound of formula I ferbam B-163 a compound of formula I mancozeb B-164 a compound of formula I maneb B-165 a compound of formula I metiram B-166 a compound of formula I metam B-167 a compound of formula I Methasulphocarb B-168 a compound of formula I propineb B-169 a compound of formula I thiram B-170 a compound of formula I Zineb B-171 a compound of formula I ziram B-172 a compound of formula I diethofencarb B-173 a compound of formula I Flubenthiavalicarb B-174 a compound of formula I iprovalicarb B-175 a compound of formula I propamocarb B-176 a compound of formula I Propamocarb hydrochloride B-177 a compound of formula I 3- (4-chloro-phenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester B-178 a compound of formula I valiphenal B-179 a compound of formula I N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) -carbamic acid (4-fluorophenyl) ester B-180 a compound of formula I dodine B-181 a compound of formula I Dodine free base B-182 a compound of formula I iminoctadine B-183 a compound of formula I Iminoctadine triacetate B-184 a compound of formula I Iminoctadine-tris (albesilate) B-185 a compound of formula I guazatine B-186 a compound of formula I Guazatine acetate B-187 a compound of formula I kasugamycin B-188 a compound of formula I Kasugamycin hydrochloride hydrate B-189 a compound of formula I polyoxins B-190 a compound of formula I streptomycin B-191 a compound of formula I Validamycin A B-192 a compound of formula I binapacryl B-193 a compound of formula I dicloran B-194 a compound of formula I dinobuton B-195 a compound of formula I dinocap B-196 a compound of formula I Nitro Thal-isopropyl B-197 a compound of formula I tecnazene B-198 a compound of formula I Fentin acetate B-199 a compound of formula I Fentin chloride B-200 a compound of formula I Fentin hydroxide B-201 a compound of formula I isoprothiolane B-202 a compound of formula I dithianon B-203 a compound of formula I edifenphos B-204 a compound of formula I fosetyl B-205 a compound of formula I Fosetyl-aluminum B-206 a compound of formula I iprobenfos B-207 a compound of formula I Pyrazohos B-208 a compound of formula I Tolclofos-methyl B-209 a compound of formula I chlorothalonil B-210 a compound of formula I dichlofluanid B-211 a compound of formula I dichlorophen B-212 a compound of formula I flusulfamide B-213 a compound of formula I Hexachlorbenzene B-214 a compound of formula I pencycuron B-215 a compound of formula I Pentachlorophenol and salts thereof B-216 a compound of formula I phthalides B-217 a compound of formula I quintozene B-218 a compound of formula I Thiophanate methyl B-219 a compound of formula I tolylfluanid B-220 a compound of formula I N- (4-chloro-2-nitro-phenyl) -N-ethyl-4-methyl-benzenesulfonamide B-221 a compound of formula I Phosphoric acid and its salts B-222 a compound of formula I sulfur B-223 a compound of formula I Bordeaux broth B-224 a compound of formula I copper acetate B-225 a compound of formula I copper hydroxide B-226 a compound of formula I copper oxychloride B-227 a compound of formula I basic copper sulphate B-228 a compound of formula I biphenyl B-229 a compound of formula I bronopol B-230 a compound of formula I cyflufenamid B-231 a compound of formula I cymoxanil B-232 a compound of formula I diphenylamine B-233 a compound of formula I metrafenone B-234 a compound of formula I mildiomycin B-235 a compound of formula I Oxine-copper B-236 a compound of formula I Prohexadione-calcium B-237 a compound of formula I spiroxamine B-238 a compound of formula I tolylfluanid B-239 a compound of formula I N- (Cyclopropylmethoxyimino- (6-difluoro-methoxy-2,3-difluoro-phenyl) -methyl) -2-phenylacetamide B-240 a compound of formula I N '- (4- (4-chloro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methyl formamidine B-241 a compound of formula I N '- (4- (4-fluoro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methyl formamidine B-242 a compound of formula I N '- (2-methyl-5-trifluoromethyl-4- (3-trimethyl-silanyl-propoxy) -phenyl) -N-ethyl-N-methyl formamidine B-243 a compound of formula I N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methyl formamidine

The active ingredients II mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf. http://www.hclrss.demon.co.uk/index.html ); they are commercially available. The compounds named after IUPAC, their preparation and their fungicidal action are also known [cf. EP-A 226 917 ; EP-A 10 28 125 ; EP-A 10 35 122 ; EP-A 12 01 648 ; WO 98/46608 ; WO 99/24413 ; WO 03/14103 ; WO 03/053145 ; WO 03/066609 ; WO 04/049804 ].

Farther the present invention relates to a pharmaceutical agent, the at least one inventive pyrazine and / or a pharmaceutically acceptable salt thereof and optionally at least one pharmaceutically acceptable carrier contains. The invention also relates to the pharmaceutical Use of the pyrazines of the invention Formula I, in particular that in the preceding description as preferably described pyrazines of the formula I, and / or pharmaceutically acceptable salts thereof, in particular their use for the preparation a drug for the treatment of cancer.

The pyrazines of the formula I according to the invention, in particular the pyrazines of the formula I according to the invention described in the preceding description, and / or their pharmaceutically acceptable salts, effectively inhibit the growth and / or proliferation of tumor cells, as in standard tests on tumor cell lines, such as HeLa , MCF-7 and COLO 205 can be shown. In particular, the pyrimidines of the formula I according to the invention generally exhibit IC ₅₀ values <10 ^-6 mol / l (ie <1 μM), preferably IC ₅₀ values <10 ^-7 mol / l (ie <100 nM) for cell cycle inhibition in HeLa cells.

The pyrazines of the formula I according to the invention, in particular those described as preferred in the foregoing description pyrazines of the formula I, and / or their pharmaceutically acceptable salts are for treatment, inhibition or controlling the growth and / or proliferation of tumor cells and related disorders. Accordingly are they for cancer therapy in warm-blooded vertebrates, d. H. of mammals and birds, in particular in humans, but also in other mammals, in particular in use and skin, such as dog, cat, pig, ruminant (Beef, sheep, goat, bison etc.), horse and birds, like Chicken, turkey, duck, goose, guinea fowl and the like.

Especially are the pyrazines of the formula of the invention I, especially those in the preceding description as preferred described pyrazines according to the invention of the formula I, and / or their pharmaceutically acceptable salts for the therapy of cancer or cancerous diseases of the following Organs suitable: chest, lung, intestine, prostate, skin (melanoma), kidney, Bladder, mouth, larynx, esophagus, stomach, ovaries, pancreas, Liver and brain.

The pharmaceutical agents according to the invention in addition to the inventive pyrazine I and / or their pharmaceutically acceptable salt at least optionally a suitable carrier. Suitable carriers are for example, those for pharmaceutical formulations usually used solvents, carriers, excipients, Binders and the like, hereinafter referred to as individual Administration modes are described by way of example.

The Compounds I according to the invention can be be administered in the usual way, for. Oral, intravenous, intramuscularly or subcutaneously. For oral administration For example, the active ingredient may be an inert diluent or mixed with an edible carrier; he can embedded in a hard or soft gelatin capsule, into tablets pressed or mixed directly with the food / feed. Of the Active ingredient can be mixed with excipients and in the form of indigestible Tablets, buccal tablets, troches, pills, capsules, suspensions, Juices, syrups and the like can be administered. Such Preparations should contain at least 0.1% active substance. The composition Of course, the preparation can vary. Usually contains 2 to 60 wt .-% of active ingredient, based on the Total weight of the respective preparation (dosing unit). preferred Preparations of the compound of the invention I contain 10 to 1000 mg of active ingredient per oral dosage unit.

The Tablets, troches, pills, capsules and the like can also contain the following constituents: binders, such as tragacanth, acacia, corn starch or gelatin, excipients, such as dicalcium phosphate, disintegrants, such as cornstarch, Potato starch, alginic acid and the like, Lubricants, such as magnesium stearate, sweetener, such as sucrose, lactose, or saccharin, and / or flavorings, like peppermint, vanilla and the like. Capsules can also contain a liquid carrier. Other substances that change the nature of the dosing unit, can be used. For example, you can Tablets, pills and capsules containing shellac, sugar or mixtures be covered by it. Syrups or juices can be next to it add sugar (or other sweeteners) to the active substance, Methyl or propylparaben as preservative, a dye and / or a flavoring. Of course you have to the constituents of the active compound preparations in the used Men tions be pharmaceutically pure and non-toxic. Furthermore you can the active substances as controlled-release preparations, z. As a sustained-release preparations formulated.

The active substances can also be administered parenterally or intraperitoneally. Solutions or Sus pensions of the active ingredients or their salts can be prepared with water using suitable wetting agents, such as hydroxypropylcellulose. Dispersions can also be made with glycerin, liquid polyethylene glycols, and mixtures thereof in oils. Often these preparations also contain a preservative to prevent the growth of microorganisms.

For Injection preparations include sterile aqueous Solutions and dispersions and sterile powders for the production sterile solutions and dispersions. The preparation must be sufficiently fluid so that it is injectable. It must be stable under the conditions of manufacture and storage and protected against contamination with microorganisms be. The carrier may be a solvent or a dispersion medium, e.g. As to water, ethanol, polyols (eg glycerol, propylene glycol or liquid polyethylene glycol), Mixtures thereof and / or vegetable oils.

Examples of the Effect against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:
The active ingredients were formulated separately as stock solution with a concentration of 10,000 ppm in DMSO.

Application Example 1 - Activity against the cause of the Septoria leaf drought Septoria tritici in the microtiter test

The Stock solution is pipetted into a microtiter plate (MTP) and with a malt-based aqueous mushroom nutrient medium diluted to the specified drug concentration. Subsequently the addition of an aqueous spore suspension of Septoria tritici. The plates were placed in a water vapor-saturated chamber set up at temperatures of 18 ° C. With an absorbance photometer MTPs were measured at 405 nm on the 7th day after inoculation.

The measured parameters were consistent with the growth of drug-free Control variant (100%) and the fungus and drug-free blank offset the relative growth in% of pathogens in the individual To determine active ingredients.

Application Example 2 - Activity against the cause of the gray mold Botrytis cinerea in the microtiter test

The Stock solution is pipetted into a microtiter plate (MTP) and with a malt-based aqueous mushroom nutrient medium diluted to the specified drug concentration. Subsequently the addition of an aqueous spore suspension of Botrytis was carried out cinerea. The plates were placed in a water vapor-saturated chamber set up at temperatures of 18 ° C. With an absorbance photometer MTPs were measured at 405 nm on the 7th day after inoculation.

The measured parameters were consistent with the growth of drug-free Control variant and the fungus and active ingredient-free blank value, relative growth in% of the pathogens in the individual drugs to investigate.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (12)

Pyrazines of the formula I,

in which the substituents have the following meaning: R ¹ , R ^{4 are} independently halogen, cyano or C ₁ -C ₈ alkoxy; or phenyl-C ₁ -C ₄ -alkyl; R ^{2 is} C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₂ -C ₁₀ -haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkenyl, C ₃ -C ₁₂ cycloalkenyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₁₂ halocycloalkenyl, aryl or aromatic heterocycle containing besides carbon atoms one to four nitrogen atoms or zero to two nitrogen atoms and one sulfur or oxygen atom as ring members, wherein the aromatic groups represent five-, six-, seven-, eight-, nine- or ten-membered ring systems; and R ² may contain one, two, three or four identical or different R ^a groups which are independently selected from: R ^a cyano, nitro, hydroxy, carboxyl, C ₁ -C ₆ -alkyl, C ₂ -C ₆ - Alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl, C ₁ -C ₆ -alkoxy, C ₂ -C ₆ -alkenyloxy, C ₃ -C ₆ -alkynyloxy, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ cycloalkenyloxy, C (O) R ^Π , C (O) OR ^Π , C (S) OR ^Π , C (O) SR ^Π , C (S) SR, OC (O) OR ^Π , C C ₁ -C ₆ -alkylthio, amino, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylene, oxy-C ₁ -C ₄ -alkylene, oxy-C ₁ - C ₃ alkyleneoxy, wherein divalent groups may be attached to the same atom or to adjacent atoms, phenyl, naphthyl, five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle, in addition to Carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members; R ^Π C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkenyl; wherein the aliphatic, alicyclic or aromatic groups in the aforementioned groups R ^a and R ^{Π in} turn be partially or fully halogenated and / or one, two or three groups R ^{b can} carry: R ^{b is} halogen, cyano, nitro, hydroxy, mercapto, amino , Carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyl, aminothiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, wherein the alkyl groups in these groups contain 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these groups contain 2 to 8 carbon atoms; Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl-C ₁ -C ₆ -alkoxy, aryl-C ₁ -C ₆ -alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members, the hetaryl radicals contain 5 or 6 ring members, wherein the cyclic systems may be partially or completely halogenated and / or substituted by alkyl or haloalkyl groups; R ^{3 is} aryl or heteroaryl containing, in addition to carbon atoms, one to four nitrogen atoms or zero to two nitrogen atoms and one sulfur or oxygen atom as ring members, the groups being five-, six-, seven-, eight-, nine- or ten-membered ring systems which in addition to a group L ¹ ortho to the bond to the pyridazine skeleton, at least one further group L _{m can} carry: L ^{1 is} halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl; L is halogen, hydroxy, cyanato (OCN), cyano, nitro, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -halocycloalkyl, C ₃ -C ₆ -cycloalkenyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -haloalkoxy, C ₂ -C ₁₀ - Alkenyloxy, C ₂ -C ₁₀ alkynyloxy, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkenyloxy, amino, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ ) alkylamino, C ( O) -R ^Φ , C (S) -R ^Φ , S (O) _n -R ^Φ ; C ₁ -C ₈ alkoxyimino (C ₁ -C ₈ ) alkyl, C ₂ -C ₁₀ alkenyloxyimino (C ₁ -C ₈ ) alkyl, C ₂ -C ₁₀ alkynyloxyimino (C ₁ -C ₈ ) -alkyl, C ₂ -C ₁₀ -alkynylcarbonyl, C ₃ -C ₆ -cycloalkylcarbonyl, or a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S; R ^{Φ is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyloxy, C ₂ -C ₄ -alkynyloxy; wherein the groups R ^Φ may be substituted by one, two or three identical or different groups R ^b as defined above; n is zero, 1 or 2; m is 1, 2, 3 or 4; and agriculturally acceptable salts thereof. Compounds of formula I according to claim 1, wherein R ¹ and R ^{4 is} halogen. Compounds of formula I according to claim 1 or 2, wherein R ^{2 is} aryl. Compounds of formula I according to any one of claims 1 to 3, wherein R ^{3 is} aryl. Process for the preparation of compounds of the formula I according to Claim 2, characterized in that compounds of the formula II

reacted with halogenating agents, which compounds II by reacting compounds of formula III

are obtained with hydrazine, which compounds of formula III by oxidative cyclization of compounds of formula IV

by condensation of carboxylic acids of formula V

with halides of the formula VI,

in which X is halogen. Compounds of the formula II according to claim 5th Fungicidal agent containing a solid or liquid Carrier and a compound of formula I according to one of claims 1 to 4. Composition according to claim 7, comprising another active ingredient. Seed containing a compound of formula I. according to any one of claims 1 to 4 in an amount of 1 to 1000 g per 100 kg. Method of combating phytopathogenic Harmful fungi, characterized in that the mushrooms, or the against fungal infestation to be protected materials, plants, the Soil or seed with an effective amount of a compound of the formula I according to one of the claims 1 to 4 treated. Pharmaceutical agent comprising at least one A compound of the formula I as defined in one of claims 1 to 4 and / or at least one pharmaceutical acceptable salt thereof and optionally at least a pharmaceutically acceptable carrier. Use of the compounds according to one of claims 1 to 4 or their pharmaceutically acceptable Salts for the manufacture of a medicament for the treatment of cancer.