Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

Definitions

• the present invention relates to thiadiazolyloxyphenylamidines of general formula (I), to a process for their preparation, to the use of the amidines according to the invention for controlling unwanted microorganisms, and to an agent for this purpose comprising the thiadiazolyloxyphenylamidines according to the invention. Furthermore, the invention relates to a method for controlling unwanted microorganisms by applying the erf ⁇ ndungswashen compounds on the microorganisms and / or in their habitat.
• WO-A-00/046184 discloses the use of amidines as fungicides.
• WO-A-03/093 224 discloses the use of arylamidine derivatives as fungicides.
• WO-A-03/024 219 discloses fungicidal compositions comprising at least one N2-phenylamidine derivative in combination with another selected known active ingredient.
• WO-A-04/037 239 discloses antifungicidal drugs based on N2-phenylamidine derivatives.
• WO-A-07/031 513 discloses thiadiazolyl-substituted phenylamidines and their preparation and use as fungicides.
• the object of the present invention is therefore to provide amidines having improved fungicidal activity.
• R 1 is selected from hydrogen; linear, branched Ci. ⁇ -alkyl, C 2 -U -
• N, O, P and S may be replaced and all of the aforementioned groups with one or more groups selected from - R ', -X, -OR', -SR ', -NR' 2 , -SiR ' 3 , -COOR ', -CN and -CONR' 2 may be substituted, wherein R 'is hydrogen or a Ci.i 2 alkyl group; SH; -SR ", wherein R" is a Ci.n-alkyl group having one or more groups selected from - R ', -X, -OR', -SR ', -NR' 2 , -SiR ' 3 , -COOR', -CN and-CONR ' 2 , wherein R' has the above meanings;
• R 2 is selected from linear, branched Ci. ⁇ -alkyl, C 2 -i 2 alkenyl, C 2 -12 alkynyl, cyclic C 3-8 allyl, C 4-8 alkenyl, C 4-8 acyclic or C5 -I8 -
• Aryl, C 7- i 9 aralkyl or C 7 .i 9 alkaryl groups wherein the ring system all of the cyclic groups mentioned above one or more carbon atoms are replaced by heteroatoms selected from N, O, P and S, substituted and all of the aforementioned groups having one or more groups selected from -R ', -X, -OR', -SR ', -NR' 2 , -SiR ' 3 , -COOR', -CN and
• one or more C atoms can be replaced by heteroatoms selected from N, O, P and S, and all the abovementioned groups having one or more groups which are selected from -R ', -X, -OR ', -SR', -NR ' 2) -SiR' 3 , -COOR ', -CN and -C0NR' 2 , wherein R 'has the above meanings;
• R 1 and R 3 together with the atoms to which they are attached or with others
• Atoms selected from N, O, P and S can form a four- to seven-membered ring which may be substituted with R ', OR', SR ', NR' 2 , SiR ' 3 groups where R 'has the above meanings;
• R 4 is selected from the group consisting of hydrogen, -X, -
• R 5 and R 6 are independently selected from hydrogen, linear, branched C 1-I2 -AIlCyI-, C 2 i 2 alkenyl, C 2 i 2 alkynyl, cyclic C 3-I 2 - alkyl, C 4- i 2 alkenyl, C. 4 ] 2- alkynyl or C 5 _i 8 -aryl, C 7-19 -aralkyl or
• C 7 .i 9 -Alkaryl groups wherein in the ring system of all the aforementioned cyclic groups, one or more C atoms may be replaced by heteroatoms selected from N, O, P and S, and all of the aforementioned groups having one or more groups which are selected from -R ', halogen (-X), alkoxy (-OR'), thioether or mercapto
• R ' is selected from the group consisting of hydrogen, halogen (-X),
• halogens includes those elements selected from the group consisting of fluorine, chlorine, bromine and iodine, with fluorine, chlorine and bromine being preferred and fluorine and chlorine being particularly preferred preferably used.
• Optionally substituted groups may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
• Alkyl groups substituted by one or more halogen atoms are for example selected from trifluoromethyl (CF 3 ), difluoromethyl (CHF 2 ), CF 3 CH 2 , ClCH 2 , CF 3 CCl 2 .
• alkyl groups are, unless otherwise defined, linear, branched or cyclic hydrocarbon groups which optionally have one, two or more single or double unsaturations or one, two or more heteroatoms which are selected from O, N, P and S may have.
• R' is hydrogen or a Ci. ⁇ - alkyl group, preferably C 2 .io-alkyl group, particularly preferred C 3 . 8- alkyl group which may have one or more heteroatoms selected from N, O, P and S.
• the definition Q-Cn-alkyl includes the largest range defined herein for an alkyl group.
• this definition includes, for example, the meanings methyl, ethyl, n-, iso-propyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3- Dimethylbutyl, n-heptyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
• Alkenyl groups are in the context of the present invention, unless otherwise defined, linear, branched or cyclic hydrocarbon groups containing at least one simple unsaturation (double bond) and optionally one, two or more single or double unsaturations or one, two or may have a plurality of heteroatoms selected from O, N, P and S.
• R' is hydrogen or a Ci. ⁇ -alkyl group, preferably C 2 .io-alkyl group, particularly preferably C 3 _g-alkyl group containing one or more heteroatoms selected from N, O , P and S
• C 2 -C 2 -alkenyl includes the widest range defined for an alkenyl group. Specifically, this definition includes, for example, the meanings vinyl; Allyl (2-propenyl), isopropenyl (1-methylethenyl); But-1-enyl (crotyl), but-2-enyl, but-3-enyl; Hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl, hex-5-enyl; Hept-1-enyl, hept-2-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl, hept-6-enyl; Oct-1-enyl, oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl, oct-7-
• Alkynyl groups are in the context of the present invention, unless otherwise defined, linear, branched or cyclic hydrocarbon groups containing at least two-fold unsaturation (triple bond) and optionally one, two or more single or double unsaturations or one, two or may have a plurality of heteroatoms selected from O, N, P and S.
• the definition C 2 -C 2 -AIkUIyI includes the widest range defined for an alkynyl group. Specifically, this definition includes, for example, the meanings ethynyl (acetylenyl); Prop-1-ynyl and prop-2-ynyl.
• C 3 -C 8 cycloalkyl includes monocyclic saturated hydrocarbon groups having 3 to 8 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• Cs.ig-aryl covers the largest range defined herein for an aryl group having 5 to 18 skeleton atoms, wherein the C atoms may be exchanged for heteroatoms.
• this definition includes, for example, the meanings cyclopentadienyl, phenyl, cycloheptatrienyl, cyclooctatetraenyl, naphthyl and anthracenyl; 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3 Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imid
• C 7 .i 9 aralkyl group includes the largest range defined herein for an arylalkyl group having a total of 7 to 19 atoms in the backbone and alkylene chain. Specifically, this definition includes, for example, the meanings benzyl and phenylethyl.
• Alkylaryl groups (alkaryl groups) are in connection with the present invention, unless defined differently, by alkyl groups and substituted aryl groups having a Ci -8 -
• Heteroatoms selected from N, O, P and S may have.
• C 7- i 9 alkylaryl group includes the widest range defined for an alkylaryl group having 7 to 19 atoms in the backbone and alkyl chain. Specifically, this definition includes, for example, the meanings tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl.
• alkyl, alkenyl, alkynyl, aryl, alkaryl and aralkyl groups may have one or more heteroatoms which, unless otherwise defined, are selected from N, O, P and S.
• the heteroatoms replace the numbered carbon atoms ,
• the compounds of the invention may be prepared as mixtures of various possible isomeric forms, particularly stereoisomers, e.g. E and Z, threo and erythro, as well as optical isomers, but optionally also of tautomers. Both the E and the Z isomers, as well as the threo and erythro, as well as the optical isomers, any mixtures of these isomers, as well as the possible tautomeric forms disclosed and claimed.
• amidines according to the invention are compounds of the formula (I)
• R 1 is selected from hydrogen; linear, branched Ci. ⁇ alkyl, C 2 _i 2 alkenyl, C 2 i 2 alkynyl or cyclic C 3-8 alkyl, C. 4 8 alkenyl, C 4 .
• R 2 is selected from linear, branched Ci.i 2 alkyl, C 2 -i 2- alkenyl, C 2 -i 2 -alkynyl, cyclic C 3-8 -AllCyI, C 4- g alkenyl, C 4-8 alkynyl or Cs.is-aryl, C 7- i -Ar- 9 alkyl- or C 7- i 9 alkaryl groups wherein the ring system all of the cyclic groups mentioned above one or more C atoms may be replaced by heteroatoms selected from N, O, P and S, and all the aforementioned groups having one or more groups selected from - R ', -X, -OR', -SR ', -NR' 2 -SiR ' 3 , -COOR', -CN and -C0NR ' 2 , wherein R' has the above meanings;
• R ', -X, -OR', -SR ', -NR' 2 , -SiR ' 3 , -COOR', -CN and -CONR ' 2 may be substituted, wherein R' has the above meanings;
• R 2 and R 3 , R 2 and R 1 or R 1 and R 3 together with the atoms to which they are attached or with further atoms selected from N, O, P and S, a four - form a seven-membered ring which may be substituted by R ', OR', SR ', NR' 2 , SiR ' 3 groups, R' being as defined above;
• R 4 is selected from the group consisting of hydrogen, -X,
• Alkaryl groups wherein in the ring system of all the aforementioned cyclic groups, one or more C atoms may be replaced by heteroatoms selected from N, O, P and S, and all of the aforementioned groups having one or more groups selected from R ', halo (-X), alkoxy (-OR'), thioether or mercapto (-SR '), amino (-NR' 2 ), silyl (-SiR ' 3 ), carboxyl ( -COOR '),
• R 5 and R 6 are independently selected from hydrogen, linear, branched Ci.i 2 alkyl, C 2 i 2 alkenyl, C 2 i 2 alkynyl, C 3- i 2 cyclic alkyl , C ⁇ ⁇ -alkenyl, C 2 4 alkynyl or C i 5- i 8 aryl, C 7 i 9 aralkyl or C 7 i 9 -alkaryl groups, where in
• one or more C atoms can be replaced by heteroatoms selected from N, O, P and S, and all the abovementioned groups having one or more groups which are selected from -R ', halogen- -X), alkoxy (-OR '), thioether or mercapto (-SR'), amino (-NR ' 2 ), silyl (-SiR' 3 ), carboxyl (-COOR '), cyano - (-CN) and amide
• R 5 and R 6 may be taken together with the C atom to which they are attached or with further atoms selected from N, O, P and S. form a three- to seven-membered ring which may be substituted with R ', OR', SR ', NR' 2 , SiR ' 3 groups, wherein R' has the above meanings;
• R 7 is selected from the group consisting of hydrogen, halogen (-X), alkoxy
• R 1 is selected from the group consisting of hydrogen, a mercapto group (-SH) or C 1-8 alkyl groups;
• R 2 is selected from linear or branched Ci. 8- alkyl groups
• R 3 is selected from linear, branched and alicyclic C 1-6 alkyl groups
• R 2 and R 3 together with the N-atom to which they are attached or with further atoms selected from N and O, can form a five- to six-membered ring containing one or more a plurality of Ci -12- alkyl groups may be substituted;
• R 4 is selected from the group consisting of -X (halogen), linear or branched, Ci.i 2 alkyl groups and Ci -5- haloalkyl groups
• R 5 and R 6 are independently selected from hydrogen, linear C ] -8 -alkyl groups;
• R 7 is selected from the group consisting of hydrogen, linear, branched, alicyclic or heterocyclic Ci.i 2 alkyl groups, halogen atoms and Ci -4 - haloalkyl groups;
• R 1 is selected from the group consisting of hydrogen, mercapto and methyl
• R 2 is selected from the group consisting of methyl and ethyl
• R 3 is selected from the group consisting of methyl, ethyl and isopropyl
• R 2 and R 3 together with the N atom to which they are attached, form a piperidyl, pyrrolidyl or 2,6-dimethylmorpholinyl radical;
• R 4 is selected from the group consisting of Cl and F atoms and -CF 3 , -CF 2 H and a methyl group;
• R 5 and R 6 are independently selected from hydrogen, methyl and ethyl groups, or together with the carbon atom to which they are attached form a cyclopropyl ring;
• R 7 is selected from the group consisting of tert-butyl, methoxy, ethoxy,
• the two radicals R 7 are preferably in the 1,4-, 2,5-, 3,5- or 2,6-position of the phenyl ring.
• the present invention further relates to the salts, N-oxides, metal complexes of the compounds described above and their stereoisomers.
• the compounds of the formula (I) have acidic or basic properties and can form salts with inorganic or organic acids or with bases or with metal ions, optionally also internal salts or adducts.
• the metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and lead, and the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper, Zinc and others into consideration. Particularly preferred are the metal ions of the elements of the fourth period.
• the metals can be present in the various valences that belong to them.
• Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (C 1 -C 4 ) -alkyl groups, mono-, , Di- and trialkanolamines of (C 1 -C 4 ) -alkanols, choline and chlorocholine.
• inorganic acids examples include hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid and acid salts such as NaHSO 4 and KHSO 4 .
• Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid and glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl groups with 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic groups such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl groups having 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as Phenyl and naphthyl, which carry one or two phosphonic acid groups) into consideration
• amidines in the context of the present invention are selected from the group consisting of: N '- (4 - ⁇ [3- (4-chlorobenzyl) -1,2,4-thiadiazol-5-yl] oxy ⁇ -2, 5-dimethylphenyl) -N-ethyl-N-methylimidoformamide (Example 1); 4 - ⁇ [3- (4-chlorobenzyl) -1,2,4-thiadiazol-5-yl] oxy ⁇ -2,5-dimethyl-N- (piperidin-1-ylmethylidene) aniline (Example 2); N '- (5-Chloro-4- ⁇ [3- (4-chlorobenzyl) -l, 2,4-thiadiazol-5-yl] oxy ⁇ -2-methylphenyl) -N-ethyl-N-methylimidoformamide (Example 3 ); 5-Chloro-4-
• amidines according to the invention can be obtained by the process illustrated in the following Schemes (Ia) and (Ib):
• nitrobenzene derivatives of the formula (III) are reacted with thiadiazolyl alcohols of the formula (II) or the alkoxides formed therefrom in accordance with the reaction scheme below to give nitrophenyl ethers of the formula (VI):
• leaving group Z all substituents are suitable which have sufficient nucleofugicity under the prevailing reaction conditions.
• halogens, triflate, mesylate, tosylate or SO 2 Me may be mentioned as suitable leaving groups.
• the reaction is preferably carried out in the presence of a base.
• bases are organic and inorganic bases commonly used in such reactions.
• bases are used, which are selected for example from the group consisting of hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates and bicarbonates of alkali or alkaline earth metals.
• bases are selected for example from the group consisting of hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates and bicarbonates of alkali or alkaline earth metals.
• bases are selected for example from the group consisting of hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates and bicarbonates of alkali or alkaline earth metals.
• Particular preference is given to sodium amide, sodium hydride, lithium diisopropylamide, sodium methoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, sodium
• tertiary amines such as e.g. Trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylpyrolidone, N, N-
• DABCO diazabicyclooctane
• DBN diazabicyclononene
• DBU diazabicycloundecene
• a catalyst selected from the group consisting of palladium, copper and their salts or complexes can be used.
• the reaction of the nitrobenzene derivative with the phenol may be carried out in bulk or in a solvent; Preferably, the reaction is carried out in a solvent selected from conventional solvents which are inert under the prevailing reaction conditions.
• aliphatic, alicyclic or aromatic hydrocarbons such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, e.g.
• Chlorobenzene dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane
• Ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether (MTBE), methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole
• Nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile
• Amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone (NMP) or hexamethylphosphoric triamide; or mixtures of these with water and pure water.
• DMF N-dimethylformamide
• the reaction can be carried out in vacuo, under normal pressure or under excess pressure and at temperatures of -20 to 200 ° C., preferably the reaction is carried out at normal pressure and at temperatures of 50 to 150 ° C.
• nitrophenol derivatives of the formula (V) or the phenolates formed therefrom are reacted with thiadiazolyl derivatives of the formula (IV) according to the following reaction scheme to give nitrophenyl ethers of the formula (VI):
• step (a) With regard to reaction conditions, solvents, catalysts and suitable leaving groups, reference is made to step (a).
• anilines of the formula (VII) are reacted with thiadiazolyl alcohols of the formula (II) or the alkoxides formed therefrom according to the following reaction scheme to give aminophenyl ethers of the formula (VHI):
• step (a) With regard to reaction conditions, solvents, catalysts and suitable leaving groups, reference is made to step (a).
• aminophenols of the formula (XII) are reacted with thiadiazolyl derivatives of the formula (IV) according to the following reaction scheme to give aminophenyl ethers of the formula (VIII):
• step (e) can be carried out by all methods described in the prior art for the reduction of nitro groups.
• the reduction is carried out with stannous chloride in concentrated hydrochloric acid as described in WO-A-0 046 184.
• the reduction can also be carried out with hydrogen gas, if appropriate in the presence of suitable hydrogenation catalysts, such as, for example, Raney nickel or Pd / C.
• suitable hydrogenation catalysts such as, for example, Raney nickel or Pd / C.
• the reaction conditions are described in the prior art and familiar to the expert. If the reduction is carried out in the liquid phase, the reaction should take place in a solvent which is inert to the prevailing reaction conditions. Such is, for example, toluene.
• reaction of the aniline ethers of the formula (VIII) to give the amidines of the formula (I) according to the invention in step (f) can be carried out as described above in scheme (Ib) using various alternative methods using
• step (i) According to an embodiment of the invention represented in step (Ib) as step (i), the aniline ethers of formula (VIII) are reacted with amino acetals of formula (XIII) in which R 1 , R 2 and R 3 are as before are defined as described and R 11 and R 12 is selected from Ci.g-alkyl groups, preferably C 2 - 6 alkyl groups, more preferably from C 3-5 alkyl groups and together with the O-atoms, to which they are attached, can form a five- or six-membered ring, converted to the thiadiazolyloxyphenylamidines of the formula (I) according to the invention.
• the amino acetals of the formula (XIII) are obtainable from the formamides described in JACS, 65, 1566 (1943) by reaction with alkylating reagents, such as, for example, dimethyl sulfate.
• reaction according to step (i) is preferably carried out in the presence of an acid.
• Suitable acids are, for example, selected from the group consisting of organic and inorganic acids, with p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid (gaseous, aqueous or in organic solution) or sulfuric acid being preferred.
• step (ii) In an alternative embodiment of the invention shown in Scheme (Ib) as step (ii), the aniline ethers of formula (VIII) are reacted with amides of formula (XTV) in which the groups R 1 , R 2 and R 3 as previously defined, converted to the Thiadiazolyloxyphenylamidinen invention.
• the reaction according to step (ii) is optionally carried out in the presence of a halogenating agent.
• Suitable halogenating agents are, for example, selected from the group consisting of PCl 5 , PCl 3 , POCl 3 or SOCl 2 .
• reaction may alternatively be in the presence of a condensing agent.
• Suitable condensing agents are those which are usually used for the formation of
• Amide bonds are used; Examples which may be acid halide such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus trichloridoxid or thionyl chloride; Anhydridtruckner such as chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; Carbodiimides such as N ⁇ N'-dicyclohexylcarbodiimide (DCC) or other customary
• Condensing agents such as e.g. Phosphorus pentoxide, polyphosphoric acid, N, N'-carbodiimidazole, 2-ethoxy-N-ethoxycarbonyl-l, 2-dihydroquinoline (EEDQ), triphenylphosphine / tetrachloromethane or Bromtripyrrolidinophosphoniumhexafluorophosphat called.
• the reaction according to step (ii) is preferably carried out in a solvent which is selected from the usual, inert in the prevailing reaction conditions solvents.
• a solvent which is selected from the usual, inert in the prevailing reaction conditions solvents.
• aliphatic, alicyclic or aromatic hydrocarbons such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether (MTBE), methyl tert-amyl ether, dioxane, tetrahydr
• R 1 is hydrogen and R 8 to R 10 are independently selected from Ci.g-alkyl groups, preferably C 2 - 6 alkyl
• Groups particularly preferably from C 3-5 alkyl groups and together with the O atoms to which they are attached, can form a five- or six-membered ring, converted to the thiadiazolyloxyphenylamidines according to the invention.
• the reaction according to step (iii) is preferably carried out in a solvent which is selected from the usual, inert in the prevailing reaction conditions solvents.
• a solvent which is selected from the usual, inert in the prevailing reaction conditions solvents.
• Chlorobenzene dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane
• Ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether (MTBE), methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1, 2-diethoxyethane or anisole
• Nitriles such as acetonitrile
• Propionitrile, n- or iso-butyronitrile or benzonitrile Amides, such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone (NMP) or hexamethylphosphoric triamide; Esters, such as methyl or ethyl acetate; Sulfoxides such as dimethylsulfoxide (DMSO); Sulfones, such as sulfolane; Alcohols such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-l, 2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; or mixtures of these with water and pure water.
• Amides such as N, N-dimethylformamide (DMF
• aminophenols of the formula (Xu) can already be used.
• step (f) With regard to the reaction conditions, solvents and catalysts, reference is made to step (f).
• step (f) With regard to the reaction conditions, solvents and catalysts, reference is made to step (f).
• the amidines of the formula (XI) obtainable from step (h) can be reacted with thiadiazolyl alcohols of the formula (II) or the alkoxides formed therefrom to give the target molecules of the formula (I) according to the invention in accordance with the following reaction scheme:
• step (i) With regard to the reaction conditions, solvents and catalysts, reference is made to step (f). Step (i)
• the amidines of the formula (X) obtainable from step (g) can be reacted with thiadiazolyl derivatives of the formula (IV) to give the target molecules of the formula (I) according to the following reaction scheme:
• step (f) With regard to the reaction conditions, solvents and catalysts, reference is made to step (f) and Tables I and II.
• the final purification of the Thiadiazolyloxyphenylamidine may optionally be carried out by conventional purification methods.
• the purification is carried out by crystallization.
• the chlorides of the formula (TVa) can be converted into the alcohols of the formula (II) by acid hydrolysis.
• the carboxylic acid amides of the general formula (XVII) used can be prepared, for example, according to the instructions in Houben-Weyl VIII, p.655 et seq. Control of unwanted microorganisms
• amidines according to the invention have a strong microbicidal action and can be used for controlling unwanted microorganisms, such as fungi (fungi) and bacteria, in crop protection and in the protection of materials.
• Fungicides can be used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
• Bactericides can be used in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
• Blumeria species such as Blumeria graminis
• Podosphaera species such as Podosphaera leucotricha
• Sphaerotheca species such as Sphaerotheca fuliginea
• Uncinula species such as Uncinula necator
• Gymnosporangium species such as Gymnosporangium sabinae
• Hemileia species such as Hemileia vastatrix
• Phakopsora species such as Phakopsora pachyrhizi and Phakopsora meibomiae
• Puccinia species such as Puccinia recondita
• Uromyces species such as Uromyces appendiculatus
• Bremia species such as Bremia lactucae
• Peronospora species such as Peronospora pisi or P. brassicae
• Peronospora species such as Peronospora pisi or P. brassicae
• Phytophthora species such as Phytophthora infestans
• Plasmopara species such as Plasmopara viticola
• Pseudoperonospora species such as Pseudoperonospora humuli or
• Pythium species such as Pythium ultimum
• Alternaria species such as Alternaria solani;
• Cercospora species such as Cercospora beticola
• Cladosporium species such as Cladosporium cucumerinum
• Cochliobolus species such as Cochliobolus sativus
• Colletotrichum species such as Colletotrichum lindemuthanium
• Cycloconium species such as cycloconium oleaginum
• Elsinoe species such as Elsinoe fawcettii
• Gloeosporium species such as, for example, Gloeosporium laeticolor
• Glomerella species such as Glomerella cingulata
• Guignardia species such as Guignardia bidwelli;
• Leptosphaeria species such as Leptosphaeria maculans
• Magnaporthe species such as Magnaporthe grisea
• Mycosphaerella species such as Mycosphaerella graminicola and Mycosphaerella fijiensis
• Phaeosphaeria species such as Phaeosphaeria nodorum
• Pyrenophora species such as, for example, Pyrenophora teres
• Ramularia species such as Ramularia collo-cygni
• Rhynchosporium species such as Rhynchosporium secalis
• Septoria species such as Septoria apii
• Typhula species such as Typhula incarnata
• Venturia species such as Venturia inaequalis
• Corticium species such as Corticium graminearum
• Fusarium species such as Fusarium oxyspomm
• Gaeumannomyces species such as Gaeumannomyces graminis
• Rhizoctonia species such as Rhizoctonia solani
• Tapesia species such as Tapesia acuformis
• Thielaviopsis species such as Thielaviopsis basicola
• Ear and panicle diseases including corncob caused by e.g.
• Alternaria species such as Alternaria spp .
• Aspergillus species such as Aspergillus flavus
• Cladosporium species such as Cladosporium cladosporioides
• Claviceps species such as Claviceps purpurea; Fusarium species such as Fusarium culmorum;
• Gibberella species such as Gibberella zeae
• Monographella species such as Monographella nivalis
• Tilletia species such as Tilletia caries
• Urocystis species such as Urocystis occulta
• Ustilago species such as Ustilago nuda
• Aspergillus species such as Aspergillus flavus
• Botrytis species such as Botrytis cinerea
• Penicillium species such as Penicillium expansum and Penicillium purpurogenum
• Sclerotinia species such as Sclerotinia sclerotiorum
• Verticilium species such as Verticilium alboatrum
• Alternaria species such as Alternaria brassicicola
• Aphanomyces species such as Aphanomyces euteiches
• Ascochyta species such as Ascochyta lentis
• Aspergillus species such as Aspergillus flavus
• Cladosporium species such as Cladosporium herbarum
• Cochliobolus species such as Cochliobolus sativus
• Colletotrichum species such as Colletotrichum coccodes
• Fusarium species such as Fusarium culmorum
• Gibberella species such as Gibberella zeae
• Macrophomina species such as Macrophomina phaseolina Monographella species, such as Monographella nivalis;
• Penicillium species such as Penicillium expansum
• Phoma species such as Phoma lingam
• Phomopsis species such as Phomopsis sojae
• Phytophthora species such as Phytophthora cactorum
• Pyrenophora species such as Pyrenophora graminea
• Pyricularia species such as Pyricularia oryzae
• Pythium species such as Pythium ultimum
• Rhizoctonia species such as Rhizoctonia solani
• Rhizopus species such as Rhizopus oryzae
• Sclerotium species such as Sclerotium rolfsii
• Septoria species such as Septoria nodorum
• Typhula species such as Typhula incarnata
• Verticillium species such as Verticillium dahliae
• Nectria species such as Nectria galligena
• Monilinia species such as Monilinia laxa
• Taphrina species such as Taphrina deformans
• Esca species such as Phaeomoniella chlamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea; Flower and seed diseases, caused by eg
• Botrytis species such as Botrytis cinerea
• Rhizoctonia species such as Rhizoctonia solani
• Helminthosporium species such as Helminthosporium solani
• Xanthomonas species such as Xanthomonas campestris pv. Oryzae;
• Pseudomonas species such as Pseudomonas syringae pv. Lachrymans;
• Erwinia species such as Erwinia amylovora.
• the following diseases of soybean beans can be controlled:
• Alternaria leaf spot (Alternaria spec. Atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), Brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)) , Dactuliophora leaf spot (Dactuliophora glycines), Downy Mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), Frogeye leaf spot (Cercospora sojina), Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyllosticta sojaecola), Pod and Stem Blight (Phomopsis sojae), Powdery Milde
• Black Root Red (Calonectria crotalariae), Charcoal Red (Macrophomina phaseolina), Fusarium Blight or Wiit, Root Red, and Pod and Collar Red (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), Mycoleptodiscus Root Red (Mycoleptodiscus terrestris), Neocosmospora (Neocosmopspora vasinfecta), Pod and Stem Blight (Diaporthe phaseolorum), Stem Canker (Diaporthe phaseolorum var.
• Phytophthora red (Phytophthora megasperma), Brown Stem Red (Phialophora gregata), Pythium Red (Pythium aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Star Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Star Decay (Sclerotinia sclerotiorum), Sclerotinia Southern Blight (Sclerotinia rolfsii), Thielaviopsis Root Red (Thielaviopsis basicola).
• the active compounds according to the invention also have a strong restorative effect in plants. They are therefore suitable for mobilizing plant-own defenses against attack by unwanted microorganisms.
• plant-strengthening (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defense system of plants in such a way that the treated plants exhibit extensive resistance to these microorganisms with subsequent inoculation with undesired microorganisms.
• Undesirable microorganisms in the present case are phytopathogenic fungi, bacteria and viruses.
• the substances according to the invention can thus be used to protect plants within a certain period of time after the treatment against the infestation by the said pathogens.
• the period within which protection is provided generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active ingredients.
• the good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.
• the active compounds according to the invention can be used with particularly good success for controlling cereal diseases, such as, for example, against Puccinia species and diseases in the wine, fruit and vegetable growing, such. against Botrytis, Venturia or Alternaria species.
• the active compounds according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.
• the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of other active ingredients.
• plants and parts of plants can be treated.
• plants are understood as meaning all plants and plant populations, such as desirable and undesired wild plants or crop plants (including naturally occurring plants)
• Crop plants can be plants produced by conventional breeding and Optimization methods or by biotechnological and genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and including protected by plant breeders' rights or non-protectable plant varieties.
• Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
• the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
• the treatment according to the invention of the plants and plant parts with the active ingredients is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, spreading, spreading and in propagation material, in particular in seeds, further by single or multi-layer wrapping.
• mycotoxins include deoxynivalenol (DON), nivalenol, 15Ac-DON, 3-ac-DON, T2 and HT2 toxin, fumonisins, zearalenone, moniliformin, fusarin, diacetoxyscirpenol (DAS) , Beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, which may be caused, for example, by the following fungi: Fusarium spec., Such as Fusarium acuminatum, F.
• the substances according to the invention can be used to protect industrial materials against infestation and destruction by undesired microorganisms.
• Technical materials as used herein mean non-living materials prepared for use in the art.
• technical materials by the active compounds according to the invention before microbial change or Destruction, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastics, coolants and other materials that can be attacked or decomposed by microorganisms.
• materials to be protected are also parts of production plants, such as cooling water circuits, called, which can be affected by the proliferation of microorganisms.
• technical materials which may be mentioned are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids, particularly preferably wood.
• microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned.
• the active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
• microorganisms of the following genera There may be mentioned, for example, microorganisms of the following genera:
• Alternaria such as Alternaria tenuis
• Aspergillus such as Aspergillus niger
• Chaetomium such as Chaetomium globosum
• Coniophora like Coniophora puetana,
• Lentinus like Lentinus tigrinus
• Penicillium such as Penicillium glaucum
• Polyporus such as Polyporus versicolor
• Aureobasidium such as Aureobasidium pullulans
• Sclerophoma such as Sclerophoma pityophila
• Trichoderma like Trichoderma viride
• Escherichia like Escherichia coli
• Pseudomonas such as Pseudomonas aeruginosa
• Staphylococcus such as Staphylococcus aureus.
• the present invention relates to an agent for controlling unwanted microorganisms comprising at least one of the thiadiazolyloxyphenylamidines according to the invention.
• the thiadiazolyloxyphenylamidines according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in seed coating compositions, as well as ULV caustic and warm mist formulations.
• formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents.
• extenders that is to say liquid solvents, liquefied gases under pressure and / or solid carriers
• surface-active agents that is to say emulsifiers and / or dispersants and / or foam-forming agents.
• organic solvents can be used as auxiliary solvents.
• Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.
• aromatics such as xylene, toluene or alkylnaphthalenes
• chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
• liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
• Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates.
• Suitable solid carriers for granules are: e.g.
• Suitable emulsifiers and / or foam-forming agents are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates.
• Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.
• Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins. and synthetic phospholipids.
• Other additives may be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• the formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.
• formulations described above can be used in a method according to the invention for controlling unwanted microorganisms, in which the thiadiazolyloxyphenylamidines according to the invention are applied to the microorganisms and / or their habitat.
• the present invention therefore more particularly relates to a method of protecting seeds and germinating plants from the infestation of phytopathogenic fungi by treating the seed with an agent according to the invention.
• the invention also relates to the use of the seed treatment agents of the invention for protecting the seed and the germinating plant from phytopathogenic fungi. Furthermore, the invention relates to seed which has been treated with an agent according to the invention for protection against phytopathogenic fungi.
• One of the advantages of the present invention is that because of the particular systemic properties of the compositions of the invention, treatment of the seed with these agents not only protects the seed itself, but also the resulting plants after emergence from phytopathogenic fungi. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
• mixtures according to the invention can also be used in particular in the case of transgenic seed.
• compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture.
• these are seeds of cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, bean, coffee, turnip (eg sugarbeet and fodder), peanut, vegetables ( like tomato, cucumber, onions and lettuce), lawn and ornamental plants.
• cereals such as wheat, barley, rye, millet and oats
• corn such as wheat, barley, rye, millet and oats
• peanut like tomato, cucumber, onions and lettuce
• the agent according to the invention is applied to the seed alone or in a suitable formulation.
• the seed is treated in a condition that is so stable that no damage occurs during the treatment.
• the treatment of the seeds can be done at any time between harvesting and sowing.
• seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
• seed may be used which has been harvested, cleaned and dried to a moisture content of less than 15% by weight.
• seed may also be used which, after drying, e.g. treated with water and then dried again.
• the agents according to the invention can be applied directly, ie without containing further components and without being diluted.
• suitable Formulations and methods for seed treatment are known in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002 / 028186 A2.
• the active compound combinations that can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
• formulations are prepared in a known manner by mixing the active ingredients or combinations of active ingredients with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
• conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
• Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, CI. Pigment Red 112 and CI. Solvent Red 1 known dyes.
• Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds.
• Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
• Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
• Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
• Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and also tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
• Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
• Defoamers which may be present in the seed-dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
• Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
• Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly dispersed silicic acid.
• Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
• Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
• the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
• the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds.
• the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature.
• the seed dressing formulations which can be used according to the invention or their diluted preparations can also be used for pickling seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
• the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water all mixing devices customarily usable for the dressing can be considered.
• the seed is placed in a mixer which adds the desired amount of seed dressing formulation, either as such or after prior dilution with water, and mixes until uniformly distributing the formulation on the seed .
• a drying process follows.
• the application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the respective content of the active ingredients in the formulations and on the seed.
• the application rates of active ingredient combination are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
• amidines of the invention can be used as such or in their formulations also in admixture with known fungicides, bactericides, acaricides, nematicides or insecticides, e.g. to broaden the spectrum of action or to prevent development of resistance.
• the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad antimycotic spectrum of activity, in particular against dermatophytes and yeasts, mold and diphasic fungi (eg against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii.
• Candida species such as Candida albicans, Candida glabrata
• Epidermophyton floccosum Aspergillus species such as Aspergillus niger and Aspergillus fumigatus
• Trichophyton species such as Trichophyton mentagrophytes
• Microsporon species such as Microsporon canis and audouinii.
• the list of these fungi is by no means
• the thiadiazolyloxyphenylamidines according to the invention can therefore be used both in medical and in non-medical applications.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules.
• the application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
• the application rates can be varied within a wide range depending on the type of application.
• the application rates of active ingredient in general between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
• the application rates of active ingredient are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
• the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
• the treatment method according to the invention can be used for the treatment of genetically modified organisms (GMOs), eg. As plants or seeds are used.
• GMOs genetically modified organisms
• Genetically modified plants are plants in which a heterologous gene has been stably integrated into the genome.
• the term "heterologous gene” essentially refers to a gene which is provided or assembled outside the plant and which, when introduced into the nuclear genome, chloroplast genome or hypochondriacal genome, imparts new or improved agronomic or other properties to the transformed plant Expressing protein or polypeptide or that it is downregulating or shutting down another gene present in the plant or other genes present in the plant (for example by antisense technology, cosuppression technology or RNAi technology [RNA Interference]).
• a heterologous gene present in the genome is also referred to as a transgene.
• a transgene defined by its specific presence in the plant genome is referred to as a transformation or transgenic event.
• the treatment according to the invention can also lead to superadditive (“synergistic”) effects.
• the following effects are possible, which go beyond the expected effects: reduced application rates and / or extended spectrum of action and / or increased efficacy of the active ingredients and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low Temperatures, increased tolerance to drought or water or soil salinity, increased flowering, harvest relief, ripening, higher yields, larger fruits, greater plant height, intense green color of the leaf, earlier flowering, higher quality and / or higher nutritional value of the harvested products, higher sugar concentration in the fruits, better storage and / or processability of the harvested products.
• the active compound combinations according to the invention can also exert a strengthening effect on plants. They are therefore suitable for mobilizing the plant defense system against attack by undesirable phytopathogenic fungi and / or Microorganisms and / or viruses. This may optionally be one of the reasons for the increased effectiveness of the combinations according to the invention, for example against fungi.
• Plant-strengthening (resistance-inducing) substances in the present context should also mean those substances or combinations of substances which are able to stimulate the plant defense system such that the treated plants, when subsequently inoculated with undesirable phytopathogenic fungi and / or microorganisms and / or viruses a considerable degree of resistance to these unwanted phytopathogenic fungi and / or microorganisms and / or viruses.
• phytopathogenic fungi, bacteria and viruses are understood to be undesirable phytopathogenic fungi and / or microorganisms and / or viruses.
• the substances according to the invention can therefore be employed for the protection of plants against attack by the mentioned pathogens within a certain period of time after the treatment.
• the period of time over which a protective effect is achieved generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active substances.
• Plants and plant varieties which are preferably treated according to the invention include all plants which have genetic material conferring on these plants particularly advantageous, useful features (whether obtained by breeding and / or biotechnology).
• Plants and plant varieties which are also preferably treated according to the invention are resistant to one or more biotic stressors, i. H. These plants have an improved defense against animal and microbial pests such as nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and / or viroids.
• Plants and plant varieties which can also be treated according to the invention are those plants which are resistant to one or more abiotic stress factors.
• Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salt content, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients, or avoidance of shade.
• Plants and plant varieties which can also be treated according to the invention are those plants which are characterized by increased yield properties.
• An increased yield can in these plants z. B. based on improved plant physiology, improved plant growth and improved plant development, such as Wasservertechnischseff ⁇ zienz, water retention efficiency, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germination and accelerated Abreife.
• Yield can be further influenced by improved plant architecture (under stress and non-stress conditions), including early flowering, control of flowering for the production of hybrid seed, seedling vigor, plant size, internode number and distance, rooting, seed size, fruit size, pod size, pod or ear number, number of seeds per pod or ear, seed mass, increased seed filling, reduced seed drop , reduced pod popping and stability.
• plant architecture under stress and non-stress conditions
• Other yield-related traits include seed composition such as carbohydrate content, protein content, oil content and oil composition, nutritional value, reduction of nontoxic compounds, improved processability, and improved shelf life.
• Plants which can be treated according to the invention are hybrid plants which already express the properties of heterosis or hybrid effect, which generally leads to higher yield, higher vigor, better health and better resistance to biotic and abiotic stress factors.
• Such plants are typically produced by crossing an inbred male sterile parental line (the female crossover partner) with another inbred male fertile parent line (the male crossbred partner).
• the hybrid seed is typically harvested from the male sterile plants and sold to propagators.
• Pollen sterile plants can sometimes be produced (eg in maize) by delaving (i.e., mechanically removing male genitalia or male flowers); however, it is more common for male sterility to be due to genetic determinants in the plant genome.
• a ribonuclease such as a barnase is selectively expressed in the tapetum cells in the stamens.
• the fertility can then be restorated by expression of a ribonuclease inhibitor such as barstar in the tapetum cells.
• Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering which can be treated according to the invention are herbicide-tolerant plants, ie plants which have tolerated one or more given herbicides have been. Such plants can be obtained either by genetic transformation or by selection of plants containing a mutation conferring such herbicide tolerance.
• Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, i. H. Plants tolerant to the herbicide glyphosate or its salts.
• glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS).
• EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
• EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
• EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium, the CP4 gene of the bacterium Agrobacterium sp., The genes for a EPSPS from the petunia, for a EPSPS from the tomato or for a Encoding EPSPS from Eleusine.
• Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants which select for naturally occurring mutations of the above mentioned genes.
• herbicide-resistant plants are, for example, plants which have been tolerated to herbicides which inhibit the enzyme glutamine synthase, such as bialaphos, phosphinotricin or glufosinate.
• Such plants can be obtained by expressing an enzyme which detoxifies the herbicide or a mutant of the enzyme glutamine synthase, which is resistant to inhibition.
• an effective detoxifying enzyme is, for example, an enzyme encoding a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinotricin acetyltransferase have been described.
• hydroxyphenylpyruvate dioxygenase HPPD
• the hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate.
• Plants tolerant of HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding an imitated HPPD enzyme.
• Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes encoding certain enzymes that allow the formation of homogentisate despite inhibition of the native HPPD enzyme by the HPPD inhibitor.
• the tolerance of plants to HPPD inhibitors can also be improved by adding plants in addition to a gene coding for HPPD.
• tolerant enzyme is transformed with a gene coding for a prephenate dehydrogenase enzyme.
• herbicide-resistant plants are plants which are resistant to acetolactate synthase (ALS) -
• Inhibitors have been tolerant.
• Examples of known ALS inhibitors include sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or
• Enzyme ALS also known as acetohydroxy acid synthase, AHAS
• Enzyme ALS confer tolerance to different herbicides or groups of herbicides.
• the preparation of sulfonylurea tolerant plants and imidazolinone tolerant plants is described in International Publication WO 1996/033270.
• Other sulfonylurea and imidazolinone tolerant plants are also disclosed in e.g. WO 2007/024782 described.
• plants tolerant to imidazolinone and / or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding.
• Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which can also be treated according to the invention are insect-resistant transgenic plants, i. Plants that have been made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such insect resistance.
• insect-resistant transgenic plant includes any plant containing at least one transgene comprising a coding sequence encoding:
• an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal part thereof such as the insecticidal crystal proteins described online at: http://www.lifesci.sussex.ac.uk/Home/Neil Crickmore / Bt /, or insecticidal parts thereof, eg Proteins of the cry protein classes CrylAb, CrylAc, CrylF, Cry2Ab, Cry3Ae or Cry3Bb or insecticidal parts thereof; or
• Presence of a second crystal protein other than Bacillus thuringiensis or a part thereof is insecticidal, such as the binary toxin consisting of the crystal proteins Cy34 and Cy35; or 3) an insecticidal hybrid protein comprising parts of two different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g. The protein CrylA.105 produced by the corn event MON98034 (WO 2007/027777); or
• Transformation were induced, such as the protein Cry3Bbl in maize events MON863 or MON88017 or the protein Cry3A in the maize event MIR 604;
• VIPs vegetative insecticidal proteins
• a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin derived from the proteins VIP1A and
• a hybrid insecticidal protein comprising parts of various secreted proteins of Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins of 1) or a hybrid of the proteins of 2) above; or
• amino acids have been replaced with another amino acid to achieve higher insecticidal activity against a target insect species and / or to broaden the spectrum of the corresponding target insect species and / or due to changes induced in the coding DNA during cloning or transformation (preserving the coding for an insecticidal protein), such as the protein VIP3Aa in cotton event COT 102.
• insect-resistant transgenic plants in the present context also include any plant comprising a combination of genes encoding the proteins of any of the encode above classes 1 to 8.
• an insect-resistant plant contains more than one transgene encoding a protein of any one of the above 1 to 8 in order to extend the spectrum of the corresponding target insect species or to delay the development of resistance of the insects to the plants by use different proteins which are insecticidal for the same target insect species, but have a different mode of action, such as binding to different receptor binding sites in the insect.
• Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant of abiotic stressors. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such stress resistance. Particularly useful plants with stress tolerance include the following:
• PARP poly (ADP-ribose) polymerase
• Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which can also be treated according to the invention have a changed amount, quality and / or storability of the harvested product and / or altered characteristics of certain components of the harvested product, such as:
• Amylose / amylopectin ratio degree of branching, average chain length, side chain distribution
• Viscosity behavior, the gel strength, the starch grain size and / or Starch grain morphology is altered in comparison to the synthesized starch in wild-type plant cells or plants, so that this modified starch is better suited for certain applications.
• Wildtype plants are modified without genetic modification. Examples are plants that produce polyfructose, particularly of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1, 6-branched alpha-1,4-glucans, and plants that produce Produce alternan.
• Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering, which can also be treated according to the invention, are plants such as cotton plants with altered fiber properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered fiber properties; these include:
• plants such as cotton plants containing an altered form of cellulose synthase genes
• plants such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids
• sucrose phosphate synthase sucrose phosphate synthase
• plants such as cotton plants with increased expression of sucrose synthase
• plants such as cotton plants with modified reactivity fibers, e.g. By expression of the N-acetylglucosamine transferase gene, including nodC, and chitin synthase genes.
• Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are Plants such as oilseed rape or related Brassica plants with altered oil composition properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered oil properties; these include:
• plants such as oilseed rape plants producing oil of high oleic acid content
• plants such as rape plants that produce oil with a low linolenic acid content.
• plants such as rape plants that produce oil with a low saturated fatty acid content.
• transgenic plants which can be treated according to the invention are plants with one or more genes coding for one or more toxins, the transgenic plants offered under the following commercial names: YIELD GARD® (for example maize, cotton, Soybeans), KnockOut® (for example corn), BiteGard® (for example maize), BT-Xtra® (for example maize), StarLink® (for example corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example corn), Protecta® and NewLeaf® (potato).
• YIELD GARD® for example maize, cotton, Soybeans
• KnockOut® for example corn
• BiteGard® for example maize
• BT-Xtra® for example maize
• StarLink® for example corn
• Bollgard® cotton
• Nucotn® cotton
• Nucotn 33B® cotton
• NatureGard® for example corn
• Protecta® and NewLeaf® pot
• Herbicide-tolerant crops to be mentioned are, for example, corn, cotton and soybean varieties sold under the following tradenames: Roundup Ready® (glyphosate tolerance, for example corn, cotton, soybean), Liberty Link® (phosphinotricin tolerance, for example rapeseed) , IMI® (imidazolinone tolerance) and SCS® (sylphonylurea tolerance), for example corn.
• Herbicide-resistant plants (plants traditionally grown for herbicide tolerance) to be mentioned include the varieties sold under the name Clearfield® (for example corn).
• transgenic plants that can be treated according to the invention are plants that contain transformation events, or a combination of transformation events, and that are listed, for example, in the files of various national or regional authorities (see, for example, http: // /gmoinfo.jrc.it/gmp browse.aspx and http://www.aebios.com/dbase.php).
• Preparation Examples are plants that contain transformation events, or a combination of transformation events, and that are listed, for example, in the files of various national or regional authorities (see, for example, http: // /gmoinfo.jrc.it/gmp browse.aspx and http://www.aebios.com/dbase.php).
• the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), whose logP values are known (determination of the logP values by means of the retention times by linear interpolation between two consecutive alkanones).
• Emulsifier 1 part by weight of alkyl-aryl-polyglycol ether (polyoxyethylene (16) tristearylphenyl ether)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• compounds of the invention show 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 15, 17, 19, 22, 23, 24, 25, 26, 27, 28, 29 , 31, 32, 35, 36, 37, 38, 39, 40, 42, 43, 44, 45, 46, 47, 49, 51, 52, 54, 55, 56, 58, 59, 60, 61, 62 , 64, 65, 67, 68, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 88, 89, 90, 94, 96 , 97, 98, 99, 100, 102, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120 and 123 at a concentration of 100 ppm of active ingredient Efficiency of 70% or more.
• Example 2 Uromyces test (bean) / protective
• Emulsifier 1 part by weight of alkyl-aryl-polyglycol ether (polyoxyethylene (16) tristearylphenyl ether)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• the plants are then placed in the greenhouse at about 21 0 C and a relative humidity of about 90%.
• the compounds of the invention show 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 20, 22, 23, 24 , 25, 26, 27, 28, 31, 32, 34, 35, 36, 37, 40, 42, 43, 47, 48, 49, 50, 51, 52, 54, 55, 56, 57, 58, 59 , 60, 61, 62, 63, 64, 65, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 84, 89, 90, 93 , 94, 95, 96, 97, 98, 99, 100, 102, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120 and 123 in a Concentration of active ingredient of lOOppm an efficiency of 70% or more.
• Example 3 Sphaerotheca test (cucumber) /
• Emulsifier 1 part by weight of alkylaryl polyglycol ether (polyoxyethylene (16) tristearylphenyl ether)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• the compounds of the invention show 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24 , 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 39, 37, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 , 50, 51, 52, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76 , 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 102 , 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117,
• Emulsifier 1 part by weight of alkylaryl polyglycol ether (polyoxyethylene (16) tristearylphenyl ether)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• the compounds of the invention show 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23 , 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 49, 51 , 52, 55, 57, 58, 59, 60, 61, 62, 63, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 , 81, 82, 83, 84, 85, 89, 90, 93, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 105, 106, 107, 108, 109, 110 and 111 at an active ingredient concentration of 500 ppm, an efficiency of 70% or more.
• Example 5 Septoria tritici test (wheat) / protective
• Emulsifier 1 part by weight of alkylaryl polyglycol ether (polyoxyethylene (16) tristearylphenyl ether)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• the compounds of the invention show 1, 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 23, 24, 25, 26, 28 , 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 39, 40, 41, 42, 44, 45, 46, 47, 49, 50, 51, 52, 55, 57, 58 , 59, 60, 61, 62, 63, 64, 65, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85 , 89, 90, 94, 95, 96, 97, 98, 99, 100, 102, 104, 105, 106, 107, 108, 109,
• Emulsifier 1.5 parts by weight of polyoxyethylene alkylphenyl ether (polyoxyethylene)
• active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
• the compounds of the invention show 1, 2, 3, 5, 11, 17, 20, 24, 25, 31, 32, 35, 37, 40, 49, 52, 55, 61, 62, 64, 68, 69 , 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 89, 90, 94, 95, 97, 99, 100 and 104 at an active ingredient concentration of 500 ppm have an efficiency of 80% or more.

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• Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
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• 2009
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