DE102005021367A1 - New thiazolecarboxylic acid anilide compounds useful for combating harmful fungus, particularly Botrytis - Google Patents

Abstract

Thiazole carboxylic acid anilide compounds (I) are new. Thiazolecarboxylic acid anilide compounds of formula (I) are new. A : thiazole compounds of formulae (A1 or A2); X1F or Cl; X2halo; n : 1 or 2; m : 2 or 3; Y11-4C-(halo)alkyl, methoxy, methylthio, CN or NO2; p : 0 or 1; R1>H, halo or 1-4C-(halo)alkyl; R2H, CH3 or halo; R3H, CH3, ethyl; and W1O or S. An independent claim is included for an agent for combating harmful fungus, comprises (I) and inert additives. [Image] [Image] ACTIVITY : Fungicide. MECHANISM OF ACTION : None given.

Description

in der die Substituenten die folgende Bedeutung haben:

X₁ F, Cl;
X₂ Halogen;
n 1, 2;
m 2, 3;
Y C₁-C₄-Alkyl, C₁-C₄-Halogenalkyl, Methoxy, Methylthio, CN, NO₂;
p 0, 1;
R¹ Wasserstoff, Halogen, C₁-C₄-Alkyl, C₁-C₄-Halogenalkyl;
R² Wasserstoff, Methyl, Halogen;
R³ Wasserstoff, Methyl, Ethyl;
W O, S.The present invention relates to thiazolecarboxanilides of the formula I.

in which the substituents have the following meaning:

X ₁ F, Cl;
X _{2 is} halogen;
n 1, 2;
m 2, 3;
Y is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, methoxy, methylthio, CN, NO ₂ ;
p 0, 1;
R ^{1 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl;
R ^{2 is} hydrogen, methyl, halogen;
R ^{3 is} hydrogen, methyl, ethyl;
WO, S.

The substituents X ₁ and X _{2 may} independently of one another have different meanings in the case of multiple substitution.

It also concerns the invention process for the preparation of these compounds, they containing agents and methods of using them to combat Harmful fungi, especially botrytis.

Out the literature are Thiazolcarbonsäureanilide with fungicidal activity known. For example, in EP-A 545 099 and EP-A 589 301 biphenylanilides of this type described on the biphenyl group have a mono-substitution.

In WO 03/066609 are specific trifluoromethyl-thiazolyl-carboxanilides described and their fungicidal action.

Out WO 03/066610 are specific difluoromethyl-thiazolyl-carboxanilides described.

task The present invention was Thiazolcarbonsäureanilide with improved fungicidal activity compared to the compounds of the prior art.

Accordingly, were found the compounds I defined above.

In addition, processes for preparing these compounds, agents containing them and methods have been disclosed found to their use for controlling harmful fungi.

you receives the compounds I in general characterized in that a carboxylic acid halide of the formula II in a manner known per se (for example J. March, Advanced Organic Chemistry, 2nd ed., 382f, McGraw-Hill, 1977) in the presence a base with an aniline of formula III.

Of the Hal in the formula II is a halogen atom such as chlorine, Bromine and iodine, in particular chlorine or bromine. This conversion usually takes place at temperatures from -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C.

suitable solvent 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 methylene chloride, dimethyl sulfoxide and dimethylformamide, particularly preferably toluene, methylene chloride and tetrahydrofuran.

It can also mixtures of the solvents mentioned 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 and calcium carbonate, and alkali metal bicarbonates, such as sodium bicarbonate and organometallic compounds, especially alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride as well as alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium as well 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.

Especially Preferably, triethylamine and pyridine are used.

The Bases are generally in equimolar Quantities, based on the compound II used. But you can also in a surplus of 5 mol% to 30 mol%, preferably 5 mol% to 10 mol%, or - in the case the use of tertiary Amines - if necessary as a solvent be used.

The Educts are generally in equimolar Quantities reacted together. It can be beneficial for the yield his, II in a surplus of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on III use.

The for the Preparation of the compounds I required starting materials of the formula II and III are known or can be synthesized analogously to the known compounds (Helv. Chim. Acta, 60, 978 (1977); Zh. Org. Khim., 26, 1527 (1990); Heterocycles 26, 1885 (1987); Izv. Akad. Nauk. SSSR Ser. Khim., 2160 (1982); THL 28, 593 (1987); THL 29, 5463 (1988)).

Furthermore, it has been found that one obtains compounds of formula I characterized in that in well Carrying way carboxylic acids of formula IV with an aniline of formula III in the presence of dehydrating agents and optionally an organic base.

suitable solvent 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, and dimethyl sulfoxide and dimethylformamide, particularly preferably methylene chloride, toluene and tetrahydrofuran.

It can also mixtures of the solvents mentioned be used.

When Dehydrating agents include 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride, Carbodiimides such as N, N'-dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide, Phosphonium salts such as (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate, Bromotripyrrolidinophosphonium hexafluorophosphate, bromotris (dimethylamino) phosphonium hexafluorophosphate, Chlorotripyrrolidinophosphonium hexafluorophosphate, uronium and thiuronium salts such as O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, O- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, S- (1-oxido-2-pyridyl) -N, N, N ', N'-tetramethylthiuroniumtetrafluorborat, O- (2-Oxo 1 (2H) pyridyl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O - [(ethoxycarbonyl) cyanomethylenamino] -N, N, N ', N'-tetramethyluronium tetrafluoroborate, Carbenium salts such as (benzotriazol-1-yloxy) dipyrrolidinocarbenium hexafluorophosphate, (Benzotriazol-1-yloxy) dipiperidinocarbenium hexafluorophosphate, O- (3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, Chloro-N ', N'-bis formamidiniumtetrafluorborat (tetramethylene), Chlorodipyrrolidinocarbenium hexafluorophosphate, chloro-N, N, N ', N'-bis (pentamethylene) formamidinium tetrafluoroborate, Imidazolium salts such as 2-chloro-1,3-dimethylimidazolidinium tetrafluoroborate, preferably 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride, N, N'-dicyclohexylcarbodiimide and N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide into consideration.

When organic bases come tertiary Amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, Lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Triethylamine and pyridine are particularly preferably used. The Bases are generally in excess from 10 mol% to 200 mol%, preferably from 50 mol% to 150 mol% used on the compound IV.

The Educts are generally in equimolar Quantities reacted together. It can be beneficial for the yield be one of the compounds in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, use. The dehydrating agents are generally in excess of 5 mol% to 100 mol%, preferably 5 mol% to 60 mol% used.

The for the Preparation of the compounds I required starting materials of the formula III and IV are known or can be synthesized analogously to the known compounds.

you receives Compounds of the formula V by reacting compounds of the formula I in a known manner in the presence of a base with an alkylating agent implements.

suitable solvent 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, as well as dimethyl sulfoxide and dimethylformamide, particularly preferably diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dimethylformamide.

It can also mixtures of the solvents mentioned be used.

Suitable alkylating agents (R ³ X) include alkyl halides such as methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, methyl chloride, ethyl chloride, alkyl (perfluoroalkyl sulfonates) such as methyl trifluoromethyl sulfonate, ethyl trifluoromethyl sulfonate, alkyl (alkyl sulfonates) such as methyl methyl sulfonate, ethyl methyl sulfonate, alkyl (aryl sulfonates) such as methyl p-tolylsulfonate, ethyl p-tolylsulfonate, oxonium salts such as trimethyloxonium tetrafluoroborate and triethyloxonium tetrafluoroborate.

Especially preferred are methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, Methyl chloride and ethyl chloride.

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, Sodium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate and 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 ethoxide, potassium ethoxide, potassium tert-butoxide and into consideration.

Especially sodium carbonate, potassium carbonate, sodium hydride, Potassium hydride, butyllithium and potassium tert-butoxide used.

The Bases are generally in equimolar Quantities based on the compound I used. But you can also in a surplus of 5 mol% to 30 mol%, preferably 5 mol% to 10 mol% used become.

The Educts are generally in equimolar Quantities reacted together. It can be beneficial for the yield be the alkylating agent in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on I use.

With regard to their use in fungicidal agents, compounds of the formula I are suitable in which the substituents have the following meaning:
C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl.
C ₁ -C ₄ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 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 and pentafluoroethyl;
Halogen such as fluorine, chlorine, bromine and iodine.

Particularly preferred compounds I in terms of biological activity are those in which the substituents are the following radicals:
X ₁ F, Cl, preferably Cl;
X ₂ F, Cl, preferably F;
n 1, 2, preferably 1;
m 2, 3;
Y ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, methoxy,
preferably methyl, difluoromethyl, trifluoromethyl, methoxy;
most preferably methyl, trifluoromethyl;
p 0, 1, preferably 0;
R ^{1 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl;
preferably hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl;
very particularly preferably hydrogen, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, trifluoromethyl;
R ^{2 is} hydrogen, halogen, methyl;
preferably hydrogen, F, Cl;
most preferably hydrogen and Cl;
R ^{3 is} hydrogen, methyl;
preferably hydrogen;
WHERE.

Particular preference is given to compounds I having the following substituent combinations in which the substituents have the following meanings:
X ₁ F, Cl;
X ₂ F, Cl;
n 1, 2;
m 2, 3;
Y is methyl, difluoromethyl, trifluoromethyl, methoxy;
P 0, 1;
R ^{1 is} hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl;
R ^{2 is} hydrogen, F, Cl, methyl;
R ^{3 is} hydrogen, methyl;
WHERE.

Also preferred are the following combinations of substituents with the following meanings:
X ₁ F, Cl;
X ₂ F, Cl;
m 2, 3;
p 0;
R ^{1 is} hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl;
R ^{2 is} hydrogen, F, Cl; preferably hydrogen, Cl, methyl;
R ^{3 is} hydrogen;
WHERE.

Especially are the compounds in view of their use as fungicides of the general formulas I-A and I-B.

Table A

Table 1:

Compounds of the general formula IA in which A is A1, R ² , R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 2:

Compounds of the general formula IA in which A is A1, R ^{2 is} Cl, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 3:

Compounds of the general formula IA in which A is A1, R ^{2 is} F, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A, with the exception of lines 397 to 462.

Table 4:

Compounds of the general formula IA in which A is A1, R ^{2 is} methyl, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 5:

Compounds of the general formula IA in which A is A1, R ^{2 is} hydrogen, R ^{3 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 6:

Compounds of the general formula IA in which A is A1, R ^{2 is} hydrogen, R ^{3 is} ethyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 7:

Compounds of the general formula IA in which A is A2, R ² , R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 8:

Compounds of the general formula IA in which A is A2, R ^{2 is} Cl, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 9:

Compounds of the general formula IA in which A is A2, R ^{2 is} F, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A, with the exception of lines 397 to 462.

Table 10:

Compounds of the general formula IA in which A is A2, R ^{2 is} methyl, R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 11:

Compounds of the general formula IA in which A is A2, R ^{2 is} hydrogen, R ^{3 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 12:

Compounds of the general formula IA in which A is A2, R ^{2 is} methyl, R ^{3 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 13:

Compounds of general formula IA, wherein A is A2, R ^{2 is} hydrogen, R ^{3 is} ethyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 14:

Compounds of the general formula IA in which A is A2, R ^{2 is} methyl, R ^{3 is} ethyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 15:

Compounds of the general formula IB in which A is A1, R ^{2 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 16:

Compounds of the general formula IB in which A is A1, R ^{2 is} F and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 17:

Compounds of the general formula IB in which A is A1, R ^{2 is} Cl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 18:

Compounds of the general formula IB in which A is A1, R ^{2 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 19:

Compounds of the general formula IB in which A is A2, R ^{2 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 20:

Compounds of the general formula IB in which A is A2, R ^{2 is} F and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 21:

Compounds of the general formula IB in which A is A2, R ^{2 is} Cl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 22:

Compounds of the general formula IB in which A is A2, R ^{2 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

The Compounds I are useful as fungicides. They are distinguished by an excellent effectiveness against a broad spectrum of phytopathogenic fungi, in particular of the Ascomycetes class, Deuteromycetes, Oomycetes and Basidiomycetes. They are partly systemically effective and can used in crop protection as foliar and soil fungicides.

Special They have meaning for the fight a variety of mushrooms on different crops such as wheat, Rye, Barley, Oats, Rice, Corn, Grass, Bananas, Cotton, Soy, Coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, as well as the seeds of these Plants.

• • Alternaria-Arten an Gemüse und Obst,
• • Bipolaris- und Drechslera-Arten an Getreide, Reis und Rasen,
• • Blumeria graminis (echter Mehltau) an Getreide,
• • Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben,
• • Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen,
• • Fusarium- und Verticillium-Arten an verschiedenen Pflanzen,
• • Mycosphaerella-Arten an Getreide, Bananen und Erdnüssen,
• • Phytophthora infestans an Kartoffeln und Tomaten,
• • Plasmopara viticola an Reben,
• • Podosphaera leucotricha an Äpfeln,
• • Pseudocercosporella herpotrichoides an Weizen und Gerste,
• • Pseudoperonospora-Arten an Hopfen und Gurken,
• • Puccinia-Arten an Getreide,
• • Pyricularia oryzae an Reis,
• • Rhizoctonia-Arten an Baumwolle, Reis und Rasen,
• • Septoria tritici und Stagonospora nodorum an Weizen,
• • Uncinula necator an Reben,
• • Ustilago-Arten an Getreide und Zuckerrohr,
• • Venturia-Arten (Schorf) an Äpfeln und Birnen,
• • Phakopsora pachyrhizi, sowie
• • P. meibomiae.

In particular, they are suitable for controlling the following plant diseases:

• • Alternaria species on vegetables and fruits,
• • Bipolaris and Drechslera species on cereals, rice and turf,
• • Blumeria graminis (powdery mildew) on cereals,
• • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines,
• • Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
• Fusarium and Verticillium species on different plants
• Mycosphaerella species on cereals, bananas and peanuts,
• • Phytophthora infestans on potatoes and tomatoes,
• Plasmopara viticola on vines,
• • Podosphaera leucotricha on apples,
• Pseudocercosporella herpotrichoides on wheat and barley
• • Pseudoperonospora species on hops and cucumbers,
• Puccinia species on cereals,
• Pyricularia oryzae on rice,
• • Rhizoctonia species on cotton, rice and turf,
• • Septoria tritici and Stagonospora nodorum on wheat,
• • Uncinula necator on vines,
• • Ustilago species on cereals and sugarcane,
• • Venturia species (scab) on apples and pears,
• • Phakopsora pachyrhizi, as well
• • P. meibomiae.

The Compounds I are also suitable for fighting of harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. Wood, paper, dispersions for the paint, fibers or tissue) and in the storage protection.

The Compounds I are applied by adding the mushrooms or the pre Fungal attack 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 desired Effect between 0.01 and 2.0 kg of active ingredient per ha.

at Seed treatment are generally drug quantities of 0.001 to 10 g, preferably 0.01 to 0.5 g per kilogram 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, for example, 0.001 g in material protection 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter treated Material.

The Compounds I can in the usual Formulations are transferred, e.g. Solutions, Emulsions, suspensions, dusts, Powders, pastes and granules. The application form depends on the respective purpose; she should be fine in any case and even distribution the compound of the invention guarantee.

• – 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) und 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 example by stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

• - water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-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) and ground synthetic minerals (eg fumed silica, 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.

When surfactants Substances include alkali, alkaline earth, ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, Alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers used, also condensation products sulfonated naphthalene and naphthalene derivatives with formaldehyde, Condensation of naphthalene or Naphtalinsulfonsäure with Phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated Isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, Tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, Alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sorbitol esters, Ligninsulfitablaugen and methylcellulose into consideration.

to Production of directly sprayable Solutions, Emulsions, pastes or oil dispersions come mineral oil fractions from medium to high boiling point, such as kerosene or diesel oil, further Coal tar oils and vegetable oils or of animal origin, aliphatic, cyclic and aromatic Hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powder-, Spreaders and dusts can by mixing or co-grinding the active substances with a solid carrier getting produced.

granules, e.g. coated, impregnated and homogeneous granules be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, Calcium and magnesium sulphate, magnesium oxide, ground plastics, Fertilizer, such as. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and herbal products, such as cornmeal, tree bark, wood and Nutshell flour, cellulose powder and other solid carriers.

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)

10 Parts by weight of a compound of the invention are dissolved in water or a water-soluble solvent. alternative Wetting agents or other auxiliaries are added. When diluting in water dissolves the active substance.

B Dispersible concentrates (DC)

20 Parts by weight of a compound of the invention are dissolved in cyclohexanone with the addition of a dispersing agent e.g. Polyvinylpyrrolidone dissolved. When diluted in water gives a dispersion.

C Emulsifiable concentrates (EC)

15 Parts by weight of a compound of the invention are in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5%) solved. When diluting in water results in an emulsion.

D emulsions (EW, EO)

40 Parts by weight of a compound of the invention are in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5%) solved. This mixture is produced by means of an emulsifying machine (Ultraturax) introduced into water and brought to a homogeneous emulsion. When diluting in water results in an emulsion.

E suspensions (SC, OD)

20 parts by weight of a compound according to the invention are added with the addition of dispersing and wetting and crushed water or an organic solvent in a stirred ball mill to a fine suspension of active ingredient. Dilution in water results in a stable suspension of the active ingredient.

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

50 Parts by weight of a compound of the invention are finely ground with the addition of dispersants and wetting agents and by means of technical devices (e.g., extrusion, spray tower, Fluidized bed) as water-dispersible or water-soluble granules produced. When diluting in water results in a stable dispersion or solution of Active ingredient.

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

75 Parts by weight of a compound of the invention with the addition of dispersing and wetting agents and silica gel in a rotor-strator mill ground. When diluting in water results in a stable dispersion or solution of Active ingredient.

2. Products for the direct application

H dusts (DP)

5 Parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. You get thereby a duster.

I granules (GR, FG, GG, MG)

0.5 Gew-parts of a compound of the invention are finely ground and combined with 95.5% excipients. Common procedures are the extrusion, the spray-drying or the fluidized bed. You get thereby a granulate for the direct application.

J ULV solutions (UL)

10 Parts by weight of a compound of the invention be in an organic solvent e.g. Xylene dissolved. This preserves to get a product for the direct application.

The Active ingredients can as such, in the form of their formulations or the ones prepared from them Application forms, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, Pastes, dusts, Scattering agents, granules by spraying, misting, dusting, scattering or casting be applied. The forms of application depend entirely on the intended use; They should be possible in any case ensure the finest distribution of the active compounds according to the invention.

Aqueous application forms can from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) be prepared by the addition of water. For the preparation of emulsions, pastes or oil dispersions can the substances are dissolved as such or in an oil or solvent, by means of Wetting, adhesive, dispersing or emulsifying agent homogenized in water become. It can but also from effective substance wetting, sticking, dispersing or Emulsifiers and possibly solvents or oil existing concentrates are prepared for dilution with Water are suitable.

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

The Active ingredients can also used with great success in Ultra Low Volume (ULV) where possible is, formulations with more than 95 wt .-% active ingredient or even the active ingredient without additives deploy.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents are usually added to the compositions of the invention in Ge weight ratio 1:10 to 10: 1 mixed.

The agents according to the invention can in the application form as fungicides also together with other active ingredients present, e.g. with herbicides, insecticides, growth regulators, such as prohexadione Ca and salts, fungicides or even with fertilizers. When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases an enlargement of the fungicidal spectrum of activity.

• • Acylalanine wie Benalaxyl, Furalaxyl, Metalaxyl, Ofurace, Oxadixyl,
• • Aminderivate wie Aldimorph, Dodine, Dodemorph, Fenpropimorph, Fenpropidin, Guazatine, Iminoctadine, Spiroxamin, Tridemorph
• • Anilinopyrimidine wie Pyrimethanil, Mepanipyrim oder Cyrodinyl,
• • Antibiotika wie Cycloheximid, Griseofulvin, Kasugamycin, Natamycin, Polyoxin, Streptomycin oder Validamycin A,
• • Azole wie Bitertanol, Bromoconazol, Cyazofamide, Cyproconazol, Difenoconazole, Dinitroconazol, Enilconazol, Epoxiconazol, Etridazol, Fenbuconazol, Fluquiconazol, Flusilazol, Flutriafol, Fuberidazole, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Ipoconazol, Metconazol, Myclobutanil, Penconazol, Perfurazoate, Propiconazol, Prochloraz, Prothioconazol, Simeconazol, Tebuconazol, Tetraconazol, Thiabendazol, Triadimefon, Triadimenol, Triflumizol, Triticonazol, 5-Chloro-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluoro-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin, 2-Butoxy-6-iod-3-propyl-chromen-4-on, 3-(3-Bromo-6-fluor-2-methyl-indol-1-sulfonyl)-[1,2,4]triazol-1-Sulfonsäure dimethylamid,
• • Dicarboximide wie Iprodion, Myclozolin, Procymidon, Vinclozolin,
• • Dithiocarbamate wie Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
• • Heterocylische Verbindungen wie Anilazin, Benomyl, Boscalid, Carbendazim, Carboxin, Oxycarboxin, Cyazofamid, Dazomet, Dithianon, Ethirimol, Dimethirimol, Famoxadon, Fenamidon, Fenarimol, Fuberidazol, Flutolanil, Furametpyr, Isoprothiolan, Mepronil, Nuarimol, Octhilinone, Probenazol, Proquinazid, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam, SYP-Z048, Thiabendazol, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazol, Triforine, 3-[5-(4-Chlor-phenyl)-2,3-dimethylisoxazolidin-3-yl]-pyridin, Bupirimate,
• • Kupferfungizide wie Bordeaux Brühe, Kupferacetat, Kupferhydroxid, Kupferoxychlorid, basisches Kupfersulfat,
• • Nitrophenylderivate, wie Binapacryl, Dinocap, Dinobuton, Nitrophthal-isopropyl
• • Phenylpyrrole wie Fenpiclonil oder Fludioxonil,
• • Schwefel,
• • Organometallische Verbindungen wie Fentinsalze
• • Organophosphor Verbindungen wie, Edifenphos, Iprobenfos, Pyrazophos, Tolclofos-methyl, Fosetyl, Fosetyl-aluminium, Phosphorsäure,
• • Sonstige Fungizide wie Acibenzolar-S-methyl, Benthiavalicarb, Carpropamid, Chlorothalonil, Cyflufenamid, Cymoxanil, Dazomet, Diclomezin, Diclocymet, Diethofencarb, Ethaboxam, Fenhexamid, Fentin-Acetat, Fenoxanil, Ferimzone, Fluazinam, Fosetyl, Fosetyl-Aluminium, Iprovalicarb, Hexachlorbenzol, Metrafenon, Pencycuron, Propamocarb, Phthalid, Toloclofos-methyl, Quintozene, Zoxamid, Fluopicolide (Picobenzamid), Carpropamid, Mandipropamid, N-(2-{4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramid, N-(2-{4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramid; Furametpyr, Thifluzamid, Penthiopyrad, Fenhexamid, 3,4-Dichlor-isothiazol-5-Carbonsäure (2-cyano-phenyl)-amid, Flubenthiavalicarb, 3-(4-Chlor-phenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)-Propionsäure methyl ester, {2-Chlor-5-[1-(6-methyl-pyridin-2-ylmethoxyimino)-ethyl]-benzyl}-Carbaminsäure methyl ester, {2-Chlor-5-[1-(3-methyl-benzyloxyimino)-ethyl]-benzyl}-Carbaminsäure methyl ester, flusulfamid, phthalid, hexachlorbenzol,
• • Strobilurine wie Azoxystrobin, Dimoxystrobin, Enestroburin (SYP-Z071), Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin oder Trifloxystrobin,
• • Sulfensäurederivate wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid,
• • Zimtsäureamide und Analoge wie Dimethomorph, Flumetover oder Flumorph.

The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

• Acylalanines such as benalaxyl, furalaxyl, metalaxyl, ofurace, oxadixyl,
• • Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph
• Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,
• Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxine, streptomycin or validamycin A,
• • Azoles such as Bitertanol, Bromoconazole, Cyazofamide, Cyproconazole, Difenoconazole, Dinitroconazole, Enilconazole, Epoxiconazole, Etridazole, Fenbuconazole, Fluquiconazole, Flusilazole, Flutriafol, Fuberidazole, Hexaconazole, Hymexazole, Imazalil, Imibenconazole, Ipoconazole, Metconazole, Myclobutanil, Penconazole, Perfurazoate, Propiconazole , Prochloroconazole, simeconazole, tebuconazole, tetraconazole, thiabendazole, triadimefon, triadimol, triflumizole, triticonazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoro- phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6-iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2 -methyl-indole-1-sulfonyl) - [1,2,4] triazole-1-sulfonic acid dimethylamide,
• Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin,
• Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb,
• Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxine, cyazofamide, dazomet, dithianone, ethirimol, dimethirimol, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, octhilinone, probenazole, proquinazide, Pyrifenox, pyroquilon, quinoxyfen, silthiofam, SYP-Z048, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine, 3- [5- (4-chloro-phenyl) -2,3-dimethylisoxazolidin-3-yl] - pyridine, bupirimate,
• Copper fungicides such as Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate,
• Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl
• Phenylpyrroles such as fenpiclonil or fludioxonil,
• • sulfur,
• Organometallic compounds such as fentin salts
• Organophosphorus compounds such as, edifenphos, Iprobenfos, pyrazophos, tolclofos-methyl, fosetyl, fosetyl-aluminum, phosphoric acid,
• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, dazomet, diclomethine, diclocymet, diethofencarb, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, Hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide, fluopicolide (picobenzamide), carpropamide, mandipropamide, N- (2- {4- [3- (4-chloro-phenyl) -prop-2- ynyloxy] -3-methoxy-phenyl} -ethyl) -2-methanesulfonylamino-3-methyl-butyramide, N- (2- {4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3 methoxy-phenyl} -ethyl) -2-ethanesulfonylamino-3-methyl-butyramide; Furametpyr, thifluzamide, penthiopyrad, fenhexamide, 3,4-dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide, flubenthiavalicarb, 3- (4-chloro-phenyl) -3- (2-isopropoxycarbonylamino-3-) methylbutyrylamino) -propionic acid methyl ester, {2-chloro-5- [1- (6-methyl-pyridin-2-ylmethoxyimino) -ethyl] -benzyl} -carbamic acid methyl ester, {2-chloro-5- [1- ( Methyl 3-methyl-benzyloxyimino) -ethyl] -benzyl} -carbamate, flusulfamide, phthalide, hexachlorobenzene,
• Strobilurins such as azoxystrobin, dimoxystrobin, enestroburine (SYP-Z071), fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
• Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid,
• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.

synthesis Examples

Example 1:

Synthesis protocol: 2-Methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (4'-chloro-4,2'-difluoro-5'-methoxy-biphenyl-2-yl) -amide (Ex. 23.1):

To a solution of 0.25 g of 2-methyl-4-trifluoromethylthiazole-5-carboxylic acid and 0.24 g of triethylamine in 30 ml of dichloromethane were added at room temperature 0.32 g of 4'-chloro-4,2'-difluoro-5'-methoxybiphenyl-2-ylamine and 0.45 g Bis (2-oxo-3-oxazolidinyl) phosphoryl chloride given. The mixture was stirred at room temperature for 60 hours. After that was successively twice with dilute hydrochloric acid, twice with sodium bicarbonate solution and washed once with water. The organic phase was dried and concentrated. The crude product was purified by column chromatography with cyclohexane / methyl tert-butyl ether 1: 2 cleaned on silica gel. This gave 0.43 g of the desired Product as a brown oil.

To the rules given here were those in the following Table 23 prepared compounds of general formula I, in the A for A1 stands and W = 0.

Table 23

Examples for the Effect against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:
The active compounds were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. This solution was 1 wt .-% emulsifier Uniperol ^® EL added (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted to the desired concentration with water.

Claims (9)

Thiazolecarboxanilides of the formula I

in which the substituents have the following meaning:

X ₁ F, Cl; X _{2 is} halogen; n 1, 2; m 2, 3; Y is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, methoxy, methylthio, CN, NO ₂ ; p 0, 1; R ^{1 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl; R ^{2 is} hydrogen, methyl, halogen; R ^{3 is} hydrogen, methyl, ethyl; WO, S. Thiazolecarboxanilides of the formula I according to Claim 1, in which the substituents have the following meaning: X ₁ F, Cl; X ₂ F, Cl; n 1, 2; m 2, 3; Y is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, methoxy; p 0, 1; R ^{1 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl; R ^{2 is} hydrogen, halogen, methyl; R ^{3 is} hydrogen, methyl; WHERE. Thiazolecarboxanilides of the formula I according to one of claims 1 or 2, in which the substituents have the following meaning: X ₁ F, Cl; X ₂ F, Cl; n 1, 2; m 2, 3; Y is methyl, difluoromethyl, trifluoromethyl, methoxy; p 0, 1; R ^{1 is} hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl; R ^{2 is} hydrogen, F, Cl, methyl; R ^{3 is} hydrogen, methyl; WHERE. Thiazolecarboxanilides of the formula I according to one of Claims 1 to 3, in which the substituents have the following meaning: X ₁ F, Cl; X ₂ F, Cl; n 1, 2; m 2, 3; p 0; R ^{1 is} hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl; R ^{2 is} hydrogen, F, Cl, methyl; R ^{3 is} hydrogen; WHERE. Thiazolecarboxanilides of the formula I according to one of Claims 1 to 4, in which the substituents have the following meaning: X ₁ F, Cl; X ₂ F, Cl; n 1, 2; m 2, 3; p 0; R ^{1 is} hydrogen, F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl; R ^{2 is} hydrogen, Cl, methyl; R ^{3 is} hydrogen; WHERE; Thiazolcarbonsäureanilide of the formula I according to any one of claims 1 to 5, in which the substituent A has the meaning A1. Means to combat of harmful fungi containing a fungicidal amount of a compound of the formula I according to one the claims 1 to 5 and inert additives. Method of control of harmful fungi, characterized in that the harmful fungi, their habitat and / or the plants to be kept free of harmful fungi or materials with a fungicidally effective amount of a compound of the formula I according to one the claims 1 to 5 treated. Use of the compounds I according to one of claims 1 to 5 to combat of harmful fungi.