WO1994004509A1 - Derives de benzimidazole utilises comme agents microbicides - Google Patents

Derives de benzimidazole utilises comme agents microbicides Download PDF

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Publication number
WO1994004509A1
WO1994004509A1 PCT/EP1993/002174 EP9302174W WO9404509A1 WO 1994004509 A1 WO1994004509 A1 WO 1994004509A1 EP 9302174 W EP9302174 W EP 9302174W WO 9404509 A1 WO9404509 A1 WO 9404509A1
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WIPO (PCT)
Prior art keywords
alkyl
halogen
substituted
unsubstituted
alkoxy
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PCT/EP1993/002174
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English (en)
Inventor
Adolf Hubele
Martin Zeller
Marius Sutter
Urs Müller
Helmut Zondler
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Ciba-Geigy Ag
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Filing date
Publication date
Application filed by Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Priority to EP93919065A priority Critical patent/EP0656891A1/fr
Priority to AU49480/93A priority patent/AU4948093A/en
Priority to JP6505887A priority patent/JPH08500352A/ja
Publication of WO1994004509A1 publication Critical patent/WO1994004509A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2

Definitions

  • the present invention relates to novel benzimidazolesulfonic acid derivatives of the formula I below. It furthermore relates to the preparation of these substances and to agrochemical compositions comprising at least one of these compounds as active ingredient. The invention also relates to the preparation of the abovementioned compositions and to the use of the active ingredients or of the compositions for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
  • R 4 -SO 2 -group is in the 1- or 3-position in the benzimidazole moiety and forms pure or mixed positional isomers relative to the substituents R 1 and R 2 , the substituents being defined as follows: R 1 is R 5 -CO- or a group a) to d):
  • R 5 is defined as follows:
  • - phenyl which can be unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkoxy, cyano or nitro and which can also be bonded via a C 1 -C 4 alkylene bridge,
  • R 6 is defined as follows:
  • R 7 and R 8 independently of one another can be hydrogen; C 1 -C 8 alkyl;
  • R 9 is C 1 -C 8 alkyl
  • R 2 radicals are identical or different and are
  • R 4 is C 1 -C 6 alkyl
  • radicals or R 13 and R 14 together form a chain , in which q is the number 4 or 5; and n is 0, 1 or 2;
  • alkyl itself or as a component of a different substituent such as haloalkyl, alkoxy or haloalkoxy
  • alkoxy or haloalkoxy is to be understood as meaning, for example, the following straight-chain or branched groups, depending on the number of the carbon atoms indicated: methyl, ethyl, propyl, butyl and their isomers, isopropyl, isobutyl, sec-butyl and tert-butyl.
  • Halogen and halo are fluorine, chlorine, bromine or iodine.
  • Haloalkoxy therefore is a monohalogenated to perhalogenated alkoxy radical, such as, inter alia, OCH 2 F, OCHF 2 , OCHFCH 3 , OCH 2 CH 2 Br and OCF 2 CHFCl.
  • the compounds of the formula I are either regioisomer mixtures AB or pure regioisomers A or B.
  • the present invention relates to the isomers mentioned and to their mixtures with each other.
  • the compounds of the formula I are solids or oils which are stable at room temperature and which are distinguished by valuable microbicidal properties. They can be used preventively and curatively in the agricultural sector or related fields for controlling plant-injurious microorganisms.
  • the active ingredients of the formula I according to the invention are distinguished not only by an outstanding microbicidal, in particular fungicidal, activity, but also by the fact that they are particularly well tolerated by plants.
  • a main sub-group within the scope of the formula I are compounds in which R 1 is a group a) to d) and in which R 5 is hydrogen; C 1 -C 12 alkyl; C 1 -C 6 alkyl which is substituted by halogen, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkoxy, C 1 -C 3 alkylthio, C 3 -C 4 alkenyloxy or C 3 -C 4 alkynyloxy, or else by phenoxy or phenylthio, whose phenyl rings can be
  • R 5 is hydrogen
  • C 1 -C 8 alkyl which is unsubstituted or substituted by halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio,
  • C 3 -C 6 cycloalkyl which is unsubstituted or substituted by halogen or C 1 -C 4 alkyl and which can be bonded via C 1 -C 2 alkyl; or is
  • phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy,
  • R 2 is in the 6- or 7-position and is halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 4 haloalkyl or
  • R 4 is C 1 -C 4 alkyl, cyclopropyl or -N(R 13 )R 14 ) in which R )3 and R 14 are identical or different C 1 -C 4 alkyl radicals;
  • n 0, 1 or 2
  • R 6 , R 7 , R 8 , R 9 , R 10 and R 11 have the abovementioned meaning.
  • Preferred compounds from amongst those of group IA are those in which R 1 is in the 5-position, and
  • R 5 is hydrogen; or C 1 -C 8 alkyl which is unsubstituted or substituted by halogen or C 1 -C 3 alkoxy; or C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or C 3 -C 6 cycloalkyl, which is unsubstituted or substituted by halogen or C 1 -C 4 alkyl and which can be bonded via C 1 -C 2 alkyl; or is phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy,
  • R 2 radicals are identical or different and are halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • n 0, 1 or 2;
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is N(R 13 )(R 14 ), in which R 13 and R 14 are as defined under group IA, and
  • R 6 is hydrogen, C 1 -C 8 alkyl or C 2 -C 8 alkenyl (compound group IB1).
  • Important oximes within group IB 1 which must be mentioned are those compounds in which
  • R 1 is a group a) which is in the 5-position
  • R 5 is C 1 -C 8 alkyl which can be unsubstituted or substituted by halogen or C 1 -C 3 alkoxy; or phenyl which can be unsubstituted or substituted by halogen;
  • R 2 radicals are identical or different and are halogen, C 1 -C 4 alkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • n 0 or 1
  • R 3 is cyano or -CSNH 2 ;
  • R 4 is N(R 13 )(R 14 ), in which R 13 and R 14 are C 1 -C 4 alkyl;
  • R 6 is hydrogen, C 1 -C 8 alkyl or C 2 -C 8 alkenyl (compound group IC1).
  • Preferred oxime derivatives within the last-mentioned group IC1 are those in which R 5 is C 1 -C 8 alkyl which can be unsubstituted or substituted by halogen or C 1 -C 3 alkoxy; or is phenyl which can be unsubstituted or substituted by halogen; and
  • R 6 is C 1 -C 4 alkyl
  • R 1 , n, R 3 and R 4 have the abovementioned meanings (compound group ID1).
  • One of the preferred sub-groups within ID1 are those in which
  • R 5 is C 1 -C 8 alkyl
  • R 2 is halogen: R 4 is dimethylamino;
  • R 6 is methyl (compound group Id).
  • R 1 is in the 5-position
  • R 5 is hydrogen
  • R 3 is cyano or -CS-NH 2 (thioamide).
  • n O or 1;
  • R 2 , R 4 and R 6 to R 1 1 are as defined for group IH1 (compound group IB2).
  • Important oximes within the last-mentioned group 1B2 are those compounds in which
  • R 6 is hydrogen; C 1 -C 8 alkyl; C 2 -C 8 alkenyl; C 3 -C 8 alkynyl; or phenyl or benzyl, whose aromatic rings are unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy C 1 -C 3 haloalkyl or C 1 -C 3 haloalkoxy; while
  • R 5 is hydrogen; or C 1 -C 5 alkyl which is unsubstituted or substituted by halogen or methoxy; or is C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 Cycloalkyl or phenyl or benzyl, whose aromatic rings can be up to disubstituted by identical or different substituents from the series consisting of chlorine, bromine, methyl, CF 3 and CF 3 O;
  • R 2 is in the 6- or 7-position and is hydrogen, halogen, methyl, methoxy, CF 3 , CF 3 O or
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is C 1 -C 4 alkyl, cyclopropyl or -N(R 13 )(R 14 ), in which R 13 and R 14 are identical or different C 1 -C 4 alkyl radicals and have a total of not more than 6 C atoms (compound group IC).
  • Preferred oxime derivatives within the last-mentioned group IC are those in which
  • R 6 is hydrogen; C 1 -C 6 alkyl; allyl; propargyl; or else phenyl or benzyl, each of which is up to trisubstituted in the ring by identical or different substituents from the series consisting of chlorine, bromine, methyl, methoxy, CF 3 , CF 3 O and CHF 2 O;
  • R 5 is hydrogen; or C 1 -C 5 alkyl which is unsubstituted or substituted by halogen or methoxy; or C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycioalkyl or phenyl or benzyl, whose aromatic rings can be up to disubstituted by identical or different substituents from the series consisting of chlorine, bromine, methyl, CF3 and CF 3 O;
  • R 2 is in the 7-position and is hydrogen, halogen, CF 3 or CHF 2 O;
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is methyl, ethyl, dimethylamino, methylethylamino or diethylamino (compound group
  • R 1 is R 5 -CO-, in which R 5 is hydrogen; C 1 -C 12 alkyl; C 1 -C 6 alkyl which is substituted by halogen, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkoxy, C 1 -C 3 alkylthio, C 3 -C 4 alkenyloxy or
  • halogen unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 3 -C 4 alkynyl which is substituted by halogen; C 3 -C 7 cycloalkyl; C 3 -C 7 cycloalkyl which is substituted by halogen, alkyl;
  • R 1 is R 5 -CO- and is in the 4- or 5-position, and in which R 5 is hydrogen; C 1 -C 8 alkyl which is unsubstituted or substituted by halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 3 -C 4 alkenyloxy or phenoxy whose phenyl moiety can be unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, OCF 3 or CF 3 ; C 2 -C 6 alkenyl; C 2 -C 4 alkynyl; C 3 -C 6 cycloalkyl which is unsubstituted or substituted by halogen or C 1 -C 4 alkyl and which can be bonded via C 1 -C 2 alkyl; or is phenyl which is unsubstituted or monosubstituted to trisub
  • IK An important sub-group of IK are compounds in which
  • R 1 is in the 5-position
  • R 5 is C 1 -C 8 alkyl which can be unsubstituted or substituted by halogen or C 1 -C 3 alkoxy;
  • R 2 radicals are identical or different and are halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or
  • n 0, 1 or 2;
  • R 3 is cyano or -CSNH 2 ;
  • R 4 is N(R 13 )(R 14 ), in which R 13 and R 14 are as defined above (compound group IKa).
  • a particularly preferred sub-group of IKa are compounds in which
  • R 5 is C 1 -C 8 alkyl which can be unsubstituted or substituted by halogen or C 1 -C 3 alkoxy; or phenyl which can be unsubstituted or substituted by halogen;
  • R 2 radicals are identical or different and are halogen, C 1 -C 4 alkyl, C 1 -C 2 alkoxy or
  • n 0 or 1
  • R 4 is N(R 13 )(R 14 ) in which R 13 and R 14 are C 1 -C 4 alkyl (compound group IKc).
  • Preferred compounds within sub-group IKc are those in which
  • R 5 is C 1 -C 8 alkyl
  • R 2 is halogen
  • R 4 is dimethylamino (compound group IKd).
  • IH2 Another important sub-group of IH2 are compounds in which R 1 is in the 4- or 5-position and
  • R 5 is hydrogen; C 1 -C 6 alkyl which is unsubstituted or substituted by halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 3 -C 4 alkenyloxy or by phenoxy whose phenyl moiety can be
  • C 3 -C 6 cycloalkyl which is unsubstituted or substituted by halogen or C 1 -C 4 alkyl and which can be bonded via C 1 -C 2 alkyl; or is phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkyl and C 1 -C 3 haloalkoxy and which can be bonded via a C 1 -C 4 alkyl bridge;
  • R 2 is in the 6- or 7-position and is halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy;
  • R 4 is C 1 -C 4 alkyl, cyclopropyl or N(R 13 )(R 14 ), in which R 13 and R 14 are identical or different C 1 -C 4 alkyl radicals;
  • n 0, 1 or 2 (compound group 1Kb).
  • a particularly important sub-group of 1Kb are compounds in which
  • R 1 is in the 5-position
  • R 5 is hydrogen
  • R 3 is cyano or -CS-NH 2 (thioamide).
  • n O or 1;
  • R 2 and R 4 are as defined for group 1Kb (compound group IKe).
  • One of the important sub-groups within formula I and group IH2 are those compounds in which R 3 is -CSNH 2 (compound group IKg).
  • One of the important sub-groups within the formula I and group 1Kb are those compounds in which R 3 is -CSNH 2 (thioamide) (compound group IKf).
  • R 9 is C 2 -C 6 alkenyl; C 2 -C 6 alkynyl or C 1 -C 6 alkyl, which is unsubstituted or substituted by C 1 -C 4 alkoxy or halogen; or in which
  • R 10 and R 11 are the substituents of these rings and independently of one another are hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by halogen, hydroxyl, C 1 -C 3 alkoxy; while
  • R 5 is hydrogen; or is C 1 -C 5 alkyl which is unsubstituted or substituted by halogen or methoxy; or is C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl or phenyl or benzyl, whose aromatic rings can be up to disubstituted by identical or different substituents from the series consisting of chlorine, bromine, methyl, CF 3 and CF 3 O;
  • R 2 is in the 6- or 7-position and is hydrogen, halogen, methyl, methoxy, CF 3 , CF 3 O or
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is C 1 -C 4 alkyl, cyclopropyl or -N(R 13 )(R 14 ), in which R 13 and R 14 are identical or different C 1 -C 4 alkyl and together have not more than 6 C atoms (compound group IE).
  • R 5 is hydrogen; or is C 1 -C 5 alkyl which is unsubstituted or substituted by halogen or methoxy; or is C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl or phenyl or benzyl, whose aromatic rings can be up to disubstituted by identical or different substituents from the series consisting of chlorine, bromine, methyl, CF 3 and CF 3 O;
  • R 2 is in the 7 -position and is hydrogen, halogen, CF 3 or CHF 2 O;
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is methyl, ethyl, dimethylamino, methylethylamino or diethylamino (compound group IF).
  • R 7 and Rg independently of one another are hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
  • C 3 -C 6 alkynyl or phenyl it being possible for the phenyl ring to be up to disubstituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, CF 3 , CF 3 O, CHF 2 O; and in which one of R 7 and R 8 can be an aliphatic, araliphatic or aromatu acyl radical having not more than 8 carbon atoms; while
  • R 5 is hydrogen; or C 1 -C 5 alkyl which is unsubstituted or substituted by halogen or methoxy; or is C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl or phenyl or benzyl, whose aromatic rings can be up to disubstituted by identical or different substituents from the series consisting of chlorine, bromine, methyl, CF 3 , CF 3 O;
  • R 2 is in the 7 -position and is hydrogen, halogen, CF 3 or CHF 2 O;
  • R 3 is cyano or -CS-NH 2 ;
  • R 4 is methyl, ethyl, dimethylamino, methylethylamino or diethylamino.
  • the compounds of the formula I can be prepared by reacting a compound of the formula II
  • R 1 , R 2 , R 3 and n are as defined in formula I and M is hydrogen or an alkali metal, preferably lithium, sodium or potassium, and Q is a leaving group, for example a halogen atom, preferably chlorine, bromine or the radical R 4 -SO 2 -O-, in an inert solvent, if desired in the presence of a base, at temperatures from -30° to +180°C, preferably -10° to 80°C, under atmospheric pressure, reduced pressure or elevated pressure, preferably at atmospheric pressure.
  • suitable inert solvents are: aliphatic, cycloaliphatic or aromatic hydrocarbons, for example hexane, cyclohexane, toluene, xylene, petroleum ether or ligroin; chlorinated hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride or chlorobenzene; ethers, for example diethyl ether, diisopropyl ether, furan, tetrahydrofuran or dioxane; ketones, for example acetone, or methyl ethyl ketone; alcohols, for example methanol, ethanol or isopropanol; esters, for example ethyl acetate or butyl acetate;
  • nitriles for example acetonitrile or propionitrile
  • acid amides for example
  • bases or acid-binding agents are hydroxides, carbonates, hydrogen carbonates or alcoholates of the alkali metals and alkaline earth metals; furthermore alkali metal hydrides, for example sodium hydride, and tertiary amines, for example
  • polar solvents for example alcohols, such as ethanol
  • acid amides for example dimethylformamide (DMF)
  • dialkylamine for example diethylamine
  • pyridine a tert-amine, such as trialkylamine.
  • H 2 S is passed in at -20° to +80°C, in particular -10° to +40°C.
  • the substituted isothioamide group it can be advantageous to use a procedure in which the sulfonylated 2-cyanobenzimidazole of the formula I' is treated with the thiol HS-R' in a polar aprotic solvent (such as acetonitrile) in the presence of weak bases (such as alkali metal carbonate) at -20° to +100°C, preferably -10° to +40°C.
  • a polar aprotic solvent such as acetonitrile
  • weak bases such as alkali metal carbonate
  • HY is an acid, preferably a hydrohalic acid, or sulfuric acid] first with trihaloimidate of the formula V in an organic solvent, such as ethers, for example diethyl ether, dioxane or
  • esters for example ethyl acetate, alcohols, for example methanol or ethanol, or preferably in glacial acetic acid, at temperatures between -20°C and +100°C, to give 2-trihalomethylbenzimidazoles of the formula VI
  • H 2 N-O-R 6 (X) in an organic solvent for example in a lower alcohol, preferably methanol, ethanol or isopropanol, if desired in a mixture with water, at temperatures between 0°C and the boiling point of the reaction mixture.
  • the hydroxylamine reagent of the formula X can be used in the form of the free base or in the form of an acid addition salt, for example in the form of the hydrochloride or the hydrogensulfate salt.
  • the oximation proceeds spontaneously or base-catalysed by adding an organic base, for example pyridine, triethylamine or 4-dimethylaminopyridine, or by adding an alkali metal carbonate or hydrogen carbonate or an alkaline earth metal carbonate or hydrogen carbonate, for example sodium carbonate or potassium carbonate. Salts of carboxylic acids, for example sodium acetate, can also be used as base;
  • the hydrazine of the formula XI can be used in the form of the free base or the acid addition salt, for example the hydrochloride or hydrogensulfate.
  • the formation of hydrazone proceeds spontaneously or base-catalysed by adding an organic base, for example pyridine, triethylamine or 4-dimethylaminopyridine, or of an alkali metal carbonate or hydrogen carbonate or an alkaline earth metal carbonate or hydrogen carbonate, for example sodium carbonate, potassium carbonate or potassium hydrogen carbonate. Salts of carboxylic acids, for example sodium acetate, can also be used as base.
  • an inert organic solvent for example in an aromatic hydrocarbon, preferably benzene, toluene or xylene, or in a halogenated hydrocarbon, preferably chloroform, at temperatures between -30°C and the boiling point of the reaction mixture, with the addition of a carboxylic acid or organic sulfonic acid, for example p-toluenesulfonic acid, or a mineral acid, for example hydrochloric acid or sulfuric acid.
  • the water of reaction which forms in this process can be removed from the reaction mixture for example by azeotropic distillation or by absorption using an alkali metal/alkaline earth metal aluminium silicate (molecular sieve).
  • GB-A-2 114567 discloses the compound
  • phytopathogenic microorganisms in particular fungi. They have highly advantageous curative and preventive properties and are used for the protection of a large number of crop plants.
  • the active ingredients of the formula I allow pests which can be found on plants or parts of plants (fruit, flowers, foliage, stalks, tubers, roots) of various crops of useful plants to be contained or destroyed, the protection against, for example,
  • novel active ingredients of the formula I prove to be effective against specific genera from the fungal class Fungi imperfecti (for example Cercospora), Basidiomycetes (for example Puccinia) and Ascomycetes (for example Erysiphe and Venturia) and, in particular, against Oomycetes (for example Plasmopara, Peronospora, Pythium and Phytophthora).
  • Fungi imperfecti for example Cercospora
  • Basidiomycetes for example Puccinia
  • Ascomycetes for example Erysiphe and Venturia
  • Oomycetes for example Plasmopara, Peronospora, Pythium and Phytophthora
  • they are therefore valuable complements of the compositions for controlling phytopathogenic fungi.
  • they advantageously have curative as well as preventative properties and can be used for the protection of a large number of crop plants.
  • the pests which can be found on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of a range of crops of useful plants are contained or destroyed by these active ingredients, the protection against, for example, phytopathogenic fungi even extending to parts of plants which are formed at a later point in time.
  • the compounds of the formula I can furthermore be used as seed-dressing agents for the treatment of seed (fruits, tubers, kernels) and plant cuttings as a protection against fungal infections and against soil-borne phytopathogenic fungi.
  • the invention also relates to the compositions which comprise, as active ingredient, compounds of the formula I, in particular crop protection products, and to their use in the agricultural sector or in related fields.
  • the present invention also provides a process for the preparation of these compositions, which comprises intimately mixing the active ingredient with one or more substances or substance groups described herein.
  • the invention furthermore provides a method of treating plants, which comprises applying the novel compounds of the formula I, or the novel compositions.
  • Target crops within the scope of this invention for the crop-protecting purpose disclosed herein are, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pome fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya beans); oil crops (oil seed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell peppers); Lauraceae (avocado, cinnamon,
  • Active ingredients of the formula I are conventionally used in the form of compositions and can be applied to the area or plant to be treated together with other active ingredients, either simultaneously or in succession.
  • These other active ingredients can be fertilizers, trace element mediators or other preparations which affect the growth of the plants.
  • Suitable carriers and additives can be solid or liquid and are substances advantageously used in the an of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
  • a preferred method of applying an active ingredient of the formula I, or an agrochemical composition comprising at least one of these active ingredients, is application to the foliage (foliar application). Frequency and rate of application will depend on the danger of infestation with the pathogen in question.
  • the compounds of the formula I can also be applied to seed kernels (coating), either by soaking the kernels in a liquid preparation of the active ingredient or by coating them with a solid preparation.
  • the compounds of the formula I are employed in an unchanged form or, preferably, together with the auxiliaries conventionally used in the art of formulation. To this end, they are advantageously processed in the known manner to give, for example, emulsion concentrates, spreadable pastes, ready-to-spray or ready-to-dilute solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or encapsulations, for example in polymeric substances.
  • the methods of application such as spraying, atomizing, dusting, scattering, brushing on or pouring, as well as the nature of the compositions, will be selected to suit the intended aims and the prevailing circumstances.
  • Favourable application rates are, as a rule, 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably 10 g to 1 kg of a.i./ha, in particular 20 g to 600 g of a.i./ha.
  • compositions, preparations or combinations comprising the active ingredient of the formula 1 with or without a solid or liquid additive are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and, if desired, surface-active compounds (surfactants).
  • extenders such as solvents, solid carriers and, if desired, surface-active compounds (surfactants).
  • aromatic hydrocarbons preferably the fractions C 8 to C 12 , such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, and water.
  • aromatic hydrocarbons preferably the fractions C 8 to C 12 , such as xylene mixtures or substituted naphthalenes
  • phthalic esters such as dibut
  • Solid carriers which are used, for example, for dusts and dispersible powders are, as a rule, ground natural minerals, such as calcite, tale, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, tale, kaolin, montmorillonite or attapulgite.
  • highly-disperse silica or highly-disperse absorptive polymers Possible paniculate, adsorptive carriers for granules are either porous types, such as pumice, brick grit, sepiolite or bentonite, or non-sorptive carrier materials, for example calcite or sand.
  • a large number of pregranulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the nature of the active ingredient of the formula I to be formulated, non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning surfactant mixtures.
  • Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
  • non-ionic surfactants examples include butyl-ionic surfactants
  • nonylphenolpolyethoxyethanols castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethylene-ethanol, polyethylene glycol and
  • Suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are mainly quaternary ammonium salts which have, as N substituents, at least one alkyl radical having 8 to 22 C atoms and, as funher substituents, lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the agrochemical preparations comprise 0.1 to 99 per cent by weight, in particular 0.1 to 95 per cent by weight, of active ingredient of the formula I, 99.9 to 1 per cent by weight, in particular 99.8 to 5 per cent by weight, of a solid or liquid additive and 0 to 25 per cent by weight, in particular 0.1 to 25 per cent by weight, of a surfactant.
  • compositions are more preferred as commercially available goods, the end consumer will, as a rule, use dilute compositions.
  • compositions can also comprise other additives, such as stabilizers, antifoams, viscosity regulators, binders or adhesives, and also fertilizers and other active ingredients for achieving specific effects.
  • additives such as stabilizers, antifoams, viscosity regulators, binders or adhesives, and also fertilizers and other active ingredients for achieving specific effects.
  • the 1 H NMR spectrum in CDCl 3 shows two signals for the proton in position 4 at 8.02 and 8.15 ppm, and the large number of signals appear double in the 13 C NMR spectrum (for example 157.6/157.4 ppm/ 142.1/141.9 ppm); accordingly, the substance is a mixture of the above isomers.
  • the active ingredient is mixed intimately with the additives and ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture on a suitable mill.
  • the active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
  • the finely ground active ingredient is applied uniformly to the kaolin which has been moistened with polyethylene glycol. Dust-free coated granules are obtained in this manner.
  • the finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Vine seedlings in the 4-5-leaf stage are sprayed with a spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed after incubation for 6 days at 95-100 % relative atmospheric humidity and 20°C. b) Residual-curative activity
  • Vine seedlings in the 4-5-leaf stage are infected with a sporangia suspension of the fungus. After incubation for 24 hours in a humid chamber at 95-100 % relative atmospheric humidity and at 20°C, the infected plants are dried and sprayed with a spray mixture (0.02 % active ingredient) prepared with a wettable powder of the active ingredient. After the spray coating has dried on, the treated plants are returned to the humid chamber. The fungus infestation is assessed 6 days after the infection.
  • Tomato plants are grown for 3 weeks and then sprayed with a spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed after incubation of the infected plants for 5 days at 90-100 % relative atmospheric humidity and 20°C. b) Systemic activity
  • Tomato plants are grown for three weeks, and a spray mixture (0.002 % of active ingredient relative to the soil volume) prepared with a wettable powder of the active ingredient is added. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed after incubation of the infected plants for 5 days at 90- 100 % relative atmospheric humidity and at 20°C.
  • 2-3-week old potato plants (cultivar Bintje) are grown for three weeks, and a spray mixture (0.002 % of active ingredient relative to the soil volume) prepared with a wettable powder of the active ingredient is added. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed after incubation of the infected plants for 5 days at 90-100 % relative atmospheric humidity and at 20°C.
  • Example B-3.4 Activity against Pythium debaryanum on sugar beet (Beta vulgaris) a) Activity after soil drench
  • the fungus is grown on sterile oat kernels and added to a mixture of soil and sand.
  • the soil which has been infected in this way is filled into flower pots, and sugar beet seeds are sown.
  • the soil is drenched (20 ppm of active ingredient relative to the soil volume) of an aqueous suspension made with test preparations formulated as wettable powders.
  • the pots are then placed in a greenhouse for 2-3 weeks at 20-24°C.
  • the soil is constantly kept uniformly moist by spraying thinly with water.
  • the fungus is grown on sterile oat kernels and added to a mixture of soil and sand.
  • the soil which has been infected in this way is filled into flower pots, and sugar beet seeds are sown, which have been dressed with the test preparations formulated as a powder for dry seed treatment (1000 ppm of active ingredient relative to the weight of the seeds).
  • the pots together with the seeds are placed in the greenhouse at 20-24°C for 2 to 3 weeks.
  • the soil is constantly kept uniformly moist by spraying thinly with water.
  • Example B-3.5 Comparison of the activities of selected acyl compounds of the formula I with the compound 1(3)-dimethylsulfamoyl-2-cyano-5-benzoylbenzimidazole (Comp. Z) of the prior art (GB-A-2 114 567).

Abstract

L'invention se rapporte à des composés représentés par la formule (I) dans laquelle R1 est un acyle, de l'oxime, du cétal ou de l'hydrazone, R2 représente halogène, nitro, ou alkyle ou alcoxy halogéné ou non, n correspond à 0, 1 ou 2, R3 représente cyano ou un groupe thioamide substitué ou non et R4 représente alkyle, cycloalkyle ou un groupe amino substitué. Ces composés qui constituent des agents microbicides efficaces peuvent être utilisés pour protéger les cultures, sous forme de compositions à formulation appropriée pour prévenir et maîtriser les maladies végétales.
PCT/EP1993/002174 1992-08-25 1993-08-16 Derives de benzimidazole utilises comme agents microbicides WO1994004509A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP93919065A EP0656891A1 (fr) 1992-08-25 1993-08-16 Derives de benzimidazole utilises comme agents microbicides
AU49480/93A AU4948093A (en) 1992-08-25 1993-08-16 Benzimidazole derivatives as microbicides
JP6505887A JPH08500352A (ja) 1992-08-25 1993-08-16 殺微生物剤としてのベンズイミダゾール誘導体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH263792 1992-08-25
CH263892 1992-08-25
CH2638/92-3 1992-08-25
CH2637/92-1 1992-08-25

Publications (1)

Publication Number Publication Date
WO1994004509A1 true WO1994004509A1 (fr) 1994-03-03

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Country Status (7)

Country Link
EP (1) EP0656891A1 (fr)
JP (1) JPH08500352A (fr)
CN (1) CN1083808A (fr)
AU (1) AU4948093A (fr)
IL (1) IL106784A0 (fr)
MX (1) MX9305135A (fr)
WO (1) WO1994004509A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996032395A1 (fr) * 1995-04-13 1996-10-17 Bayer Aktiengesellschaft Derives benzimidazole
US6297236B1 (en) 1998-04-06 2001-10-02 Bayer Aktiengesellschaft Fungicide active substance combinations

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE129147T1 (de) * 1992-01-08 1995-11-15 Nestle Sa Kosmetische und dermatologische zusammensetzung, die dioldiester enthält.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087375A1 (fr) * 1982-02-09 1983-08-31 Rhone-Poulenc Agrochimie Nouveaux dérivés du cyano-2 benzimidazole, leur préparation et leur utilisation comme fongicides et acaricides
EP0219192A2 (fr) * 1985-08-08 1987-04-22 Schering Agrochemicals Limited Fongicides
FR2601010A1 (fr) * 1986-07-02 1988-01-08 Rhone Poulenc Agrochimie Derives de sulfonyl benzimidazole, leur preparation ainsi que leur utilisation a titre de fongicides
FR2607811A1 (fr) * 1986-12-05 1988-06-10 Rhone Poulenc Agrochimie Derives de sulfonyl benzimidazole, leur preparation ainsi que leur utilisation a titre de fongicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087375A1 (fr) * 1982-02-09 1983-08-31 Rhone-Poulenc Agrochimie Nouveaux dérivés du cyano-2 benzimidazole, leur préparation et leur utilisation comme fongicides et acaricides
EP0219192A2 (fr) * 1985-08-08 1987-04-22 Schering Agrochemicals Limited Fongicides
FR2601010A1 (fr) * 1986-07-02 1988-01-08 Rhone Poulenc Agrochimie Derives de sulfonyl benzimidazole, leur preparation ainsi que leur utilisation a titre de fongicides
FR2607811A1 (fr) * 1986-12-05 1988-06-10 Rhone Poulenc Agrochimie Derives de sulfonyl benzimidazole, leur preparation ainsi que leur utilisation a titre de fongicides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996032395A1 (fr) * 1995-04-13 1996-10-17 Bayer Aktiengesellschaft Derives benzimidazole
US5925663A (en) * 1995-04-13 1999-07-20 Bayer Aktiengesellschaft Benzimidazole derivatives
US6080776A (en) * 1995-04-13 2000-06-27 Bayer Aktiengesellschaft Benzimidazole derivatives
US6235765B1 (en) 1995-04-13 2001-05-22 Bayer Aktiengesellschaft Benzimidazole derivatives
US6297236B1 (en) 1998-04-06 2001-10-02 Bayer Aktiengesellschaft Fungicide active substance combinations

Also Published As

Publication number Publication date
CN1083808A (zh) 1994-03-16
EP0656891A1 (fr) 1995-06-14
IL106784A0 (en) 1993-12-08
AU4948093A (en) 1994-03-15
JPH08500352A (ja) 1996-01-16
MX9305135A (es) 1994-05-31

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