EP0656891A1 - Derives de benzimidazole utilises comme agents microbicides - Google Patents

Derives de benzimidazole utilises comme agents microbicides

Info

Publication number
EP0656891A1
EP0656891A1 EP93919065A EP93919065A EP0656891A1 EP 0656891 A1 EP0656891 A1 EP 0656891A1 EP 93919065 A EP93919065 A EP 93919065A EP 93919065 A EP93919065 A EP 93919065A EP 0656891 A1 EP0656891 A1 EP 0656891A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
substituted
unsubstituted
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93919065A
Other languages
German (de)
English (en)
Inventor
Adolf Hubele
Martin Zeller
Marius Sutter
Urs Müller
Helmut Zondler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0656891A1 publication Critical patent/EP0656891A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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] and R 2 , the substituents being defined as follows:
  • Rj is R 5 -CO- or a group a) to d):
  • R 5 is defined as follows:
  • - C ⁇ Cgalkyl which is substituted by halogen, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkoxy, C r C 3 alkylthio, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, or else by phenoxy or phenylthio whose phenyl rings can be unsubstituted or substituted by halogen, C r C 4 alkyl, C C 4 alkoxy, C C 4 haloalkyl or C r C 4 haloalkoxy; - C -C 8 alkenyl;
  • - phenyl which can be unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, C C 3 alkyl, Cj-C 3 alkoxy, Cj-C 3 haloalkyl, C C haloalkoxy, cyano or nitro and which can also be bonded via a C r C 4 alkylene bridge, and in which
  • R 6 is defined as follows: hydrogen, C j -Cgalkyl; C 2 -C 8 alkenyl; C 2 -Cgalkynyl; benzyl or phenyl, whose aromatic ring is unsubstituted or substituted by one or more of the substituents halogen, C r C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkyl and C r C 4 haloalkoxy;
  • R 7 and R 8 independently of one another can be hydrogen; C j -Cgalkyl; C -C 8 alkenyl; C 2 -C 8 alkynyl; or benzyl or phenyl, whose aromatic ring is unsubstituted or substituted by one or more of the substituents C r C 4 haloalkoxy, C r C 4 haloalkyl, halogen, C C 4 alkyl and C r C 4 alkoxy; and in which one of the two substituents R 7 and R 8 can be an aliphatic, araliphatic or aromatic acyl radical having not more than 8 carbon atoms; or R 7 and R 8 together are ⁇ CH 2 -) ⁇ - where m is 3, 4 or 5;
  • R 5 is as defined under a) and Ro is C r C 8 alkyl; C 2 -C 8 alkenyl;
  • RJO and R u independently of one another are hydrogen, C r C 6 alkyl; or C j -C 4 alkyl which is substituted by halogen, hydroxyl or C r C 3 alkoxy, and p is the number 2 or 3;
  • R 2 radicals are identical or different and are halogen; C r C 4 alkyl; C r C 4 alkoxy; C r C 4 haloalkyl; C r C 4 haloalkoxy; nitro;
  • R 4 is C r C 6 alkyl
  • R ]3 and R ]4 are identical or different C r C 4 alkyl
  • R 14 radicals or R 13 and R 14 together form a chain - " CH 2 " ⁇ , in which q is the number 4 or 5; and n is 0, 1 or 2; with the exception of the compound l(3)-dimethylsulfamoyl-2-cyano-5-benzoyl- benzimidazole.
  • 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 , 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 is a group a) to d) and in which R 5 is hydrogen; C C 12 alkyl; C r C 6 alkyl which is substituted by halogen, C -C 4 alkoxyalkoxy, C r 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 unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkyl or C r C 4 haloalkoxy; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 3 -C alkynyl which is substituted by halogen; C 3 -C 7 cycloalkyl; C 3 -C 7 cycloalky
  • R 5 is hydrogen
  • C 3 -C 6 cycloalkyl which is unsubstituted or substituted by halogen or C C 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 j -C 3 alkyl, C j -C 3 alkoxy, C r C haloalkyl or
  • R 4 is C C 4 alkyl, cyclopropyl or -N(R ]3 )R 14 ) in which R )3 and R 14 are identical or different C r C 4 alkyl radicals; and n is 0, 1 or 2, while R 6 , R 7 , R 8 , R 9 , ] ⁇ ) and R n have the abovementioned meaning.
  • Preferred compounds from amongst those of group IA are those in which R ! is in the 5-position, and
  • R 5 is hydrogen; or C r C 8 alkyl which is unsubstituted or substituted by halogen or
  • C r C 3 alkoxy or C 2 -C 4 alkenyl, C 2 -C alkynyl or C 3 -C 6 cycloalkyl, which is unsubstituted - or substituted by halogen or C r C 4 alkyl and which can be bonded via C r 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 ⁇ alkyl, Cj-C ⁇ alkoxy, -C ⁇ haloalkyl and C r C 3 haloalkoxy and which can also be bonded via a C r C alkyl bridge;
  • R 2 radicals are identical or different and are halogen, C r C 4 alkyl, C r C 4 alkoxy or
  • 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 r C 8 alkyl or C 2 -C x alkenyl (compound group IB1).
  • Important oximes within group IB 1 which must be mentioned are those compounds in which
  • R ] is a group a) which is in the 5-position
  • R 5 is C r C 8 alkyl which can be unsubstituted or substituted by halogen or C r C 3 alkoxy; or phenyl which can be unsubstituted or substituted by halogen;
  • R 2 radicals are identical or different and are halogen, C r C 4 alkyl, C r C 2 alkoxy or
  • n O 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 r C 4 alkyl;
  • R 6 is hydrogen, -Cgalkyl or C -C 8 alkenyl (compound group ICl).
  • Preferred oxime derivatives within the last-mentioned group ICl are those in which R 5 is
  • Cj-Cgalkyl which can be unsubstituted or substituted by halogen or C C 3 alkoxy; or is phenyl which can be unsubstituted or substituted by halogen;
  • R 6 is C r C 4 alkyl
  • One of the preferred sub-groups within ID1 are those in which R 5 is C r C 8 alkyl; and R 2 is halogen: R 4 is dimethylamino; and
  • R 6 is methyl (compound group Id).
  • R j is in the 5-position
  • R 5 is hydrogen
  • R 3 is cyano or -CS-NH 2 (thioamide); and n is O or 1;
  • R 2 , R and R 6 to R n 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 j -Cgalkyl; C -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 j -C 3 alkyl, C j -C 3 alkoxy
  • R 5 is hydrogen; or C r 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 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 -C 4 alkyl, cyclopropyl or -N(R 13 )(R 14 ), in which R ] 3 and R ]4 are identical or different Cj-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 ft is hydrogen; C r C ⁇ 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 j -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 cyc oalkyl 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
  • Rj is R 5 -CO-, in which R 5 is hydrogen; C
  • R j is R 5 -CO- and is in the 4- or 5-position, and in which R s is hydrogen; C r C 8 alkyl which is unsubstituted or substituted by halogen, C r C 3 alkoxy, C r C 3 alkylthio, C 3 -C alkenyloxy or phenoxy whose phenyl moiety can be unsubstituted or substituted by halogen, C r C 4 alkyl, C j -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 alkyl and which can be bonded via C r C 2 alkyl; or is phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different
  • IK An important sub-group of IK are compounds in which
  • R j is in the 5-position
  • R 5 is Cj-Cgalkyl which can be unsubstituted or substituted by halogen or
  • R 2 radicals are identical or different and are halogen, C ] -C 4 alkyl, Cj-C alkoxy or
  • R 3 is cyano or -CSNH 2 ;
  • R is N(R 3 )(R ]4 ), 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 Cj-C 8 alkyl which can be unsubstituted or substituted by halogen or Cj-C 3 alkoxy; or phenyl which can be unsubstituted or substituted by halogen;
  • R radicals are identical or different and are halogen, C r C 4 alkyl, C r C 2 alkoxy or
  • n 0 or 1 ;
  • R 4 is N(R 13 )(Rj 4 ) in which R 13 and R 14 are C r C 4 alkyl (compound group IKc).
  • Preferred compounds within sub-group IKc are those in which
  • R 5 is C j -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 Rj is in the 4- or 5-position and
  • R 5 is hydrogen; C r C 6 alkyl which is unsubstituted or substituted by halogen, C j -C 3 alkoxy,
  • C 3 -C 6 cycloalkyl which is unsubstituted or substituted by halogen or Cj-C alkyl and which can be bonded via C j -C 2 alkyl; or is phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen,
  • R 2 is in the 6- or 7-position and is halogen, Cj-C 3 alkyl, Cj-C 3 alkoxy, Cj-C 4 haloalkyl or
  • R 4 is C r C 4 alkyl, cyclopropyl or N(R 13 )(R 14 ), in which R 13 and R 14 are identical or different C r C 4 alkyl radicals; and n is 0, 1 or 2 (compound group 1Kb).
  • a particularly important sub-group of 1Kb are compounds in which
  • R is in the 5-position
  • R 5 is hydrogen
  • R 3 is cyano or -CS-NH 2 (thioamide); and n is 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 is C 2 -C 6 alkenyl; C 2 -C 6 alkynyl or C r C 6 alkyl, which is unsubstituted or substituted by
  • RJO and RJJ are the substituents of these rings and independently of one another are hydrogen or C j -C 4 alkyl which is unsubstituted or substituted by halogen, hydroxyl,
  • R 5 is hydrogen; or is C -C ⁇ alkyl which is unsubstituted or substituted by halogen or methoxy; or is C 2 -C alkenyl, C 2 -C 4 alkynyl, Gj-CjCycloalkyl 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 j -C 4 alkyl, cyclopropyl or -N(R ] )(R 14 ), in which R 13 and R ]4 are identical or different C j -C 4 alkyl and together have not more than 6 C atoms (compound group IE).
  • R 5 is hydrogen; or is C j -C ⁇ 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 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, Cj-C 6 alkyl, C 2 -C 6 alkenyl,
  • C 3 -Cgalkynyl or phenyl it being possible for the phenyl ring to be up to disubstituted by halogen, C j -C 4 alkyl, C,-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 j -C ⁇ 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 j , 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 dimethylformamide; sulfoxides, for example dimethyl sulfoxide or sulfolane.
  • 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 triethylamine, triisopropylamine, pyridin or 4-N,N-dimethylaminopyridine.
  • alkali metal hydrides for example sodium hydride
  • tertiary amines for example triethylamine, triisopropylamine, pyridin or 4-N,N-dimethylaminopyridine.
  • R 3 -CSNH 2
  • is carried out in polar solvents (for example alcohols, such as ethanol), but preferably in acid amides, for example dimethylformamide (DMF), in the presence of an approximately equimolar amount of dialkylamine (for example diethylamine) or in pyridine using 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
  • ethers for example diethyl ether, dioxane or 1,2-dimethoxyethane
  • 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
  • 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 l(3)-dimethylsulfamoyl-2-cyano-5-benzoylbenzimidazole as fungicide 12A(B). As will be demonstrated further below, its activity is insufficient in comparison with acyl compounds of the present invention. There was therefore no reason for a person skilled in the art to synthesize precisely these acyl compounds of the formula I above, or to derivatize their carbonyl group.
  • compounds of the formula I have a biocidal spectrum which is highly favourable for practical requirements for controlling 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, phytopathogenic fungi extending even to parts of plants which are formed at a later point in time.
  • 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. Selective herbicides and insecticides, fungicides, bactericides, nematicides, moUuscicides or mixtures of a plurality of these preparations, with or without other carriers or surfactants conventionally used in the art of formulation or other application-enhancing additives can also be used.
  • 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 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 to C 12 , such as xylene mixtures or substituted naphthalenes
  • phthalic esters such as dibutyl
  • Solid carriers which are used, for example, for dusts and dispersible powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, 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 nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethylene-ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • 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 OJ to 99 per cent by weight, in particular OJ 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 OJ 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.
  • H-2 l-Dimethylsulfamoyl-2-cvano-5-butyroylbenzimidazole and 3-dimethylsulfamoyl-2-cvano-5-butyroylbenzimidazole (Comp. 1.21)
  • H-3 l-MefhylsulfonyI-2-cyano-5-butyroylbenzimidazole and 3-methylsulfonyl-2-cvano-5-butyroylbenzimidazole (Comp. 1.23)
  • Ph phenyl
  • R, CN: 9.1 -CH, 7-Cl -CH 3
  • Kaolin 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.
  • 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.
  • 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 3 weeks and then sprayed with a spray mixture (0.02 % 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.
  • 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)
  • 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 l(3)-dimethylsulfamoyl-2-cyano-5-benzoylbenzimidazole (Comp. Z) of the prior art (GB-A-2 114 567).

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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.
EP93919065A 1992-08-25 1993-08-16 Derives de benzimidazole utilises comme agents microbicides Withdrawn EP0656891A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH263792 1992-08-25
CH2638/92 1992-08-25
CH2637/92 1992-08-25
CH263892 1992-08-25
PCT/EP1993/002174 WO1994004509A1 (fr) 1992-08-25 1993-08-16 Derives de benzimidazole utilises comme agents microbicides

Publications (1)

Publication Number Publication Date
EP0656891A1 true EP0656891A1 (fr) 1995-06-14

Family

ID=25691001

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93919065A Withdrawn EP0656891A1 (fr) 1992-08-25 1993-08-16 Derives de benzimidazole utilises comme agents microbicides

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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5474775A (en) * 1992-01-08 1995-12-12 Nestec S.A. Cosmetic compositions containing 2,3-butanediol fatty acid diesters

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19513990A1 (de) * 1995-04-13 1996-10-17 Bayer Ag Benzimidazol-Derivate
US6297236B1 (en) 1998-04-06 2001-10-02 Bayer Aktiengesellschaft Fungicide active substance combinations

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2521141A1 (fr) * 1982-02-09 1983-08-12 Rhone Poulenc Agrochimie Nouveaux derives du cyano-2 benzimidazole, leur preparation et leur utilisation comme fongicides
GB8519920D0 (en) * 1985-08-08 1985-09-18 Fbc Ltd Fungicides
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9404509A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5474775A (en) * 1992-01-08 1995-12-12 Nestec S.A. Cosmetic compositions containing 2,3-butanediol fatty acid diesters

Also Published As

Publication number Publication date
MX9305135A (es) 1994-05-31
JPH08500352A (ja) 1996-01-16
AU4948093A (en) 1994-03-15
IL106784A0 (en) 1993-12-08
WO1994004509A1 (fr) 1994-03-03
CN1083808A (zh) 1994-03-16

Similar Documents

Publication Publication Date Title
KR100482919B1 (ko) 살충제로서의피리미딘-4-온유도체
JP3002786B2 (ja) 有害生物防除組成物
WO2006022225A1 (fr) Dérivé optiquement actif de phtalimide, insecticide pour l'agriculture ou l'horticulture et procédé d'utilisation de celui-ci
WO1996037472A2 (fr) Microbicides a base de pyridine
JPH0369906B2 (fr)
US5066661A (en) Agents for protecting plants against diseases
JPH01283270A (ja) 植物を病気から保護するための組成物
EP0656891A1 (fr) Derives de benzimidazole utilises comme agents microbicides
KR970000951B1 (ko) 치환된 이소니코티노일피리딘일 히드라진 유도체 및 그의 제법
KR0174026B1 (ko) 트리아졸 화합물
SK94795A3 (en) Pyrazolyl acrylic acid derivatives, intermediates in this method and their use as microbicides
JP2503547B2 (ja) カルバモイルトリアゾ―ル誘導体、その製造法およびそれを有効成分とする除草剤
PL185836B1 (pl) N-sulfonylowe pochodne aminokwasów, sposób otrzymyN-sulfonylowe pochodne aminokwasów, sposób otrzymywania N-sulfonylowych pochodnych aminokwasów orazwania N-sulfonylowych pochodnych aminokwasów orazkompozycja do zwalczania i zapobiegania inwazji fikompozycja do zwalczania i zapobiegania inwazji fitopatogennych grzybów na uprawy roślinnetopatogennych grzybów na uprawy roślinne
US5322853A (en) Microbicidal benzotriazole compounds
HUT55961A (en) Fungicide compositions containing thiazolyl-5-carbonamode derivatives as active components and process for producing the active components
RU2070197C1 (ru) Производные тиазолил-5-карбонамида, фунгицидное средство для борьбы с грибными болезнями растений, способ борьбы с грибными болезнями растений
JPH04230271A (ja) 殺微生物剤
JPH05255311A (ja) 殺微生物剤
CA2035729A1 (fr) Microbicides
AU4560593A (en) Benzimidazole derivatives as microbicides
WO1994018173A1 (fr) Derives de l'acide sulfonique de benzimidazole en tant que microbicides
WO1995001975A1 (fr) Derives de pyrimidin-4-ylaminomethylquinoleine utilises comme pesticides
GB2127820A (en) Microbicidal imidazolidine-2,4- dione derivatives
JPS6327482A (ja) 除草剤組成物
JPH069626A (ja) 殺微生物剤

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950119

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 19951220

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19960501