[go: up one dir, main page]

WO1997046535A1 - 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides - Google Patents

3-cyanoaryl-pyrazoles et leur utilisation comme herbicides Download PDF

Info

Publication number
WO1997046535A1
WO1997046535A1 PCT/EP1997/002580 EP9702580W WO9746535A1 WO 1997046535 A1 WO1997046535 A1 WO 1997046535A1 EP 9702580 W EP9702580 W EP 9702580W WO 9746535 A1 WO9746535 A1 WO 9746535A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyano
methyl
chloro
fluoro
pyrazole
Prior art date
Application number
PCT/EP1997/002580
Other languages
German (de)
English (en)
Inventor
Otto Schallner
Karl-Heinz Linker
Karl-Julius Reubke
Markus Dollinger
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to JP10500145A priority Critical patent/JP2000512275A/ja
Priority to EP97923954A priority patent/EP0906285A1/fr
Priority to BR9709521A priority patent/BR9709521A/pt
Priority to CA002256508A priority patent/CA2256508A1/fr
Priority to AU29585/97A priority patent/AU2958597A/en
Publication of WO1997046535A1 publication Critical patent/WO1997046535A1/fr

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
    • C07D405/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5

Definitions

  • the invention relates to new 3-cyanoaryl-pyrazoles, processes for their preparation, new intermediates and their use as herbicides
  • Q represents oxygen (O), sulfur (S), SO or SO 2 ,
  • R 1 represents hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,
  • R stands for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,
  • R ⁇ represents hydrogen, halogen or optionally substituted alkyl
  • R represents hydrogen or halogen and R for hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or for one of the residues -QR 6 , -NH-R 6 , -NH-OR 6 , -NH-SO 2 -R 6 , -N (SO 2 - R 6 ) 2 ,
  • Q 1 and Q 2 each represent oxygen or sulfur and R 6 represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
  • R 1 has the meaning given above
  • R is hydrogen or alkyl, preferably hydrogen or C j -C 6 - alkyl group
  • the compounds of general formula (I) can be prepared by customary methods into other compounds of general formula (I) according to the above definition Substituentendefi ⁇ converted, for example, by conventional alkylation, acylation or sulfonylation reactions rungs- (eg R 2 H ⁇ CH 3, CHF 2 'C 2 H 5 ,
  • saturated or unsaturated hydrocarbon radicals such as alkyl, alkenyl or alkynyl, are each straight-chain or branched
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
  • the invention preferably relates to compounds of the formula (I)
  • Q represents oxygen (O), sulfur (S), SO or SO 2 ,
  • R 1 for hydrogen, for optionally by cyano, halogen or CC 4 -
  • Alkoxy-substituted alkyl having 1 to 6 carbon atoms represents in each ge optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C j -C each 4 -alkyl-substituted cycloalkyl or cycloalkylalkyl having 3 each up to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
  • R 2 for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen, C ] -C 4 alkoxy or C j -C 4 alkylthio, for each optionally substituted by halogen alkenyl or alkynyl each having 2 to 6 carbon atoms , or for cycloalkyl or cycloalkylalkyl which is optionally substituted by cyano, halogen or C 1 -C 4 -alkyl and has in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
  • R 3 represents hydrogen, halogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen, CC 4 -alkoxy or C 1 -C 4 -alkylthio,
  • R 4 represents hydrogen or halogen and R 5 represents hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or one of the radicals -QR 6 , -NH-R 6 , -NH-OR 6 , -NH-SO 2 -R 6 , -N (SO 2 -R 6 ) 2 ,
  • Q 1 and Q 2 each represent oxygen or sulfur and R 6 represents optionally by cyano, halogen, C, -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylcarbonyl, C 1 -C 4 -alkoxy-carbonyl or C j -C 4 -Alkylam ⁇ no- carbonyl-substituted alkyl with 1 to 6 carbon atoms, each optionally by cyano, carboxy, halogen, C -.- C 4 -alkyl carbonyl,
  • the invention relates in particular to compounds of the formula (I)
  • Q represents oxygen (O), sulfur (S), SO or SO 2 ,
  • R 1 for hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, for each optionally by fluorine, chlorine or bromine-substituted propenyl, butenyl, propynyl or butynyl, or for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl Im optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl ethyl stands,
  • R 2 for hydrogen, for each optionally by cyano, fluorine, chlorine,
  • R 3 is hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-, which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio.
  • R 4 represents hydrogen or fluorine, chlorine or bromine and
  • R 5 for hydroxy, mercapto, amino, fluorine, chlorine, bromine or for one of the
  • Q and Q each represent oxygen or sulfur and R each optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl
  • Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl in each case optionally by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, n- or i-butyroyl , Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl substituted propenyl, butenyl, propynyl or butynyl, each optionally with cyano, carboxy, fluorine, chlorine, bromine, acetyl , Propionyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloprop
  • Thiocarbamoyl methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, methylamino, ethylamino or phenyl, phenyl, substituted or phenethylamino for each optionally by hydroxy, mercapto,
  • Formula (II) provides a general definition of the hydrazine derivatives to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I).
  • R 1 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 1
  • the starting materials of the formula (II) are known synthetic chemicals.
  • Formula (III) provides a general definition of the cyanoarylcarbonyl acetic acid derivatives to be used further as starting materials in process (a) according to the invention.
  • R 3 , R 4 and R D preferably or in particular have those meanings which are already related above with the description of the compounds of formula (I) according to the invention preferably or as particularly preferred for R, R 4 and R 5 ;
  • R preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, in particular hydrogen, methyl or ethyl.
  • the starting materials of the formula (III) are, with the exception of the compound ethyl 2- (4-cyano-2-fluorobenzoyl) acetic acid - alias ethyl 3- (4-cyano-2-fluorophenyl) -3-oxo propionate (cf. WO 96/01255) - not yet known from the literature; with the exception of 2- (4-cyano-2-fluoro-benzoyl) acetic acid ethyl ester, they are the subject of the present application as new substances.
  • R and R J have the meaning given above
  • X 1 represents halogen
  • an acid acceptor such as, for example, methylamine
  • a reaction auxiliary such as, for example, magnesium chloride
  • a diluent such as, for example, acetonitrile
  • the malonic acid derivatives of the formula (IV) required as products are known organic synthetic chemicals With the exception of the compounds 4-cyano-3-methoxy-benzoyl chloride (cf. Arch Pharm 323 (1990), 507-512; EP 166609) and 4-cyano-2-fluoro-, the cyanobenzoyl halides of the formula (V) which are further required as precursors are benzoyl chloride (cf. WO 96/01255) not yet known from the literature; With the exception of 4-cyano-3-methoxy-benzoyl chloride and 4-cyano-2-fluoro-benzoyl chloride, they are the subject of the present application as new substances
  • R 4 and R 5 have the meaning given above
  • halogenation agents such as phosgene (or its dimer or trimer) or thionyl chloride, optionally in the presence of a reaction auxiliary, such as BN, N-dimethylformamide, and optionally in the presence of a diluent, such as carbon tetrachloride, at temperatures between 0 ° C and
  • cyanobenzoic acids of the formula (VI) required as precursors are known and / or can be prepared by processes known per se (cf. Arch. Pharm 323 (1990), 507-512, Collect Czech Chem Commun 40 (1975), 3009-3019, Chem Pharm Bull 27 (1979), 3039-3048, J Chem Soc, Perkin Trans. I
  • X 2 represents halogen, in particular fluorine or chlorine
  • R 5 and X 2 have the meaning given above,
  • oxidizing agents e.g. Potassium permanganate
  • a diluent e.g. Acetone
  • X 3 represents halogen, in particular fluorine or chlorine
  • the precursors of the formula (VIII) are known and / or can be prepared by known processes (cf. EP 191 185, EP 433124, EP431373, EP 497239, EP 557949, EP 566268, EP 635486)
  • cyanobenzoic acids of the formula (Via) can also be obtained starting from known halogenated benzoic esters of the formula (IX) - see J Chem Eng Data 13 (1968), 587-588, cited in CA 69 106150 - according to the following formula scheme (R alkyl , in particular methyl or ethyl, X 3 halogen, in particular fluorine or chlorine)
  • R 3 , R 4 and R 5 have the meaning given above,
  • carbon disulfide carbon disulfide, CS 2
  • an acid acceptor such as, for example, potassium t-butoxide
  • a diluent such as, for example
  • Tetrahydrofuran and optionally subsequently - preferably without intermediate insulation - with an alkylating agent, such as methyl iodide, at temperatures between -30 ° C and + 30 ° C (see the preparation examples)
  • the precursors of the formula (X) are known and / or can be prepared by known processes (cf. Chem Pharm Bull 33 (1985), 1360-1366, EP 166609, EP 628550, WO 94/05153, production examples)
  • organic solvents include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane , Dichloromethane, chloroform, carbon tetrachloride, ether, such as
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C. and 150 ° C., preferably between 20 ° C. and 120 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under increased or reduced pressure - generally between 0.1 bar and 10 bar
  • the starting materials are generally used in approximately aquimolar amounts. However, it is also possible to use one of the components in a larger excess.
  • the reaction is generally carried out in a suitable diluent and the reaction mixture is generally carried out for several hours Stirred at the required temperature. Working up is carried out by customary methods (see the preparation examples).
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers
  • the active compounds according to the invention can be used, for example, in the following plants
  • the compounds are suitable for total weed control, for example on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa and berry fruit can also be used. and hop plants, on ornamental and sports turf and pasture land and for selective weed control in annual crops
  • the compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers
  • Fabrics are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, 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.
  • 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.
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks like
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example 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 can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be used as such or in their formulations, also in a mixture with known herbicides, for weed control, finished formulations or tank mixes being possible.
  • Acetochlor Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Asulam, Atrazine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap - ethyloylpropyl ), Bialaphos, Bifenox, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butylate, cafenstrole, Carbetamide, Chlomethoxyfen, Chloramben, Chloridazon,
  • a mixture with other known active ingredients such as fungicides, insecticides, acacids, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
  • the use is carried out in a customary manner, for example by pouring, spraying Spray, sprinkle
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing
  • the amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha
  • a mixture of 47 g (0.20 mol) of 3- (4-cyano-2,5-difluorophenyl) -5-hydroxy-1-methyl-1H-pyrazole and 350 ml of N, N-dimethylformamide is mixed with 55 g of potassium carbonate are added and the mixture is heated to 50 ° C. for about 60 minutes. Then, at an internal temperature between 60 ° C. and 70 ° C., 100 g (1.16 mol) of chlorodifluoromethane are introduced within about 6 hours. The mixture is then concentrated in a water jet vacuum and the residue is taken up in 500 ml of water. The aqueous suspension is acidified with 2N hydrochloric acid and extracted with dichloromethane.
  • the isomeric compound 3- (4-cyano-2,5-difluorophenyl) -2-difluoromethyl-l-methyl-pyrazole-5- can be extracted by column chromatography (with dichloromethane on silica gel). be isolated from the melting point 128 ° C.
  • Example 3
  • Example 47 The compound listed in Table 1 as Example 47 can be produced, for example, as follows'
  • Example 79 The compound listed in Table 1 as Example 79 can be produced, for example, as follows:
  • Example 79 The compound listed in Table 1 as Example 79 can also be prepared, for example, as follows
  • a solution of 10.9 g (0.06 mol) is added dropwise at -20 ° C. to a suspension of 13.5 g (0.12 mol) of potassium t-butoxide in 100 ml of tetrahydrofuran in about 30 minutes.
  • Example 80 The compound listed in Table 1 as Example 80 can be prepared, for example, as follows
  • Example 82 The compound listed in Table 1 as Example 82 can be made, for example, as follows
  • Example 83 The compound listed in Table 1 as Example 83 can be made, for example, as follows
  • Example 87 the compound listed in Table 1 as Example 87 can be prepared as follows
  • reaction mixture is then stirred for about 18 hours at room temperature and then concentrated.
  • the residue is mixed with 1.2 liters of toluene and then with 1 liter of 13% hydrochloric acid
  • the mixture is stirred for 3 hours at room temperature, the precipitated solid is filtered off and the organic phase is separated from the filtrate. It is washed with 13% hydrochloric acid and then with water, dried with magnesium sulfate and filtered. The solvent is carefully removed from the filtrate in a water jet vacuum distilled off.
  • the reaction mixture is poured onto 500 ml of ice water, adjusted to pH 1 with hydrochloric acid and extracted with 1500 ml of ethyl acetate.
  • the organic phase is washed with sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum.
  • the crude product obtained as a residue is stirred with about 20 ml of acetonitrile, the precipitated solid is filtered off and dried. 6.9 g (40% of theory) of l- (4-cyano-2,5-difluorophenyl) -3,3-bis (methylthio) -2-propen-l-one are obtained as a crystalline light yellow solid of Melting point 188 ° C.
  • Solvent 5 parts by weight of acetone emulsifier, 1 part by weight of alkylaryl polyglycol ether
  • Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active compound preparation, so that the desired amounts of active compound are applied per unit area.
  • the concentration of the spray series is chosen so that in each case 1000 l of water / ha desired amounts of active ingredient are applied
  • Test plants which have a height of 5-15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area.
  • the concentration of the spray mixture is chosen so that the respectively desired amounts of active compound are applied in 1000 l of water / ha

Landscapes

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

Abstract

L'invention concerne de nouveaux 3-cyanoaryl-pyrazoles de formule générale (I), dans laquelle Q représente oxygène (O), soufre (S), SO ou SO2; R1 représente hydrogène ou l'un des radicaux suivants éventuellement substitués: alkyle, alcényle, alcynyle, cycloalkyle ou cycloalkylalkyle; R2 représente hydrogène ou l'un des radicaux suivants éventuellement substitués: alkyle, alcényle, alcynyle, cycloalkyle ou cycloalkylalkyle; R3 représente hydrogène, halogène ou alkyle éventuellement substitué; R4 représente hydrogène ou halogène; et R5 représente hydrogène, hydroxy, mercapto, amino, hydroxyamino, halogène ou l'un des radicaux suivants: -Q-R?6, -NH-R6¿, -NH-O-R6, -NH-SO¿2-R?6, -N(SO¿2-R?6)2, -CQ?1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6¿, -NH-CQ1-R6, -N(SO¿2?-R?6)(CQ1-R6), -Q2-CQ1-Q2-R6¿, -NH-CQ?1-Q2-R6 ou -Q2-CQ1-NH-R6, où Q1 et Q2¿ représente oxygène ou soufre, et R6 représente l'un des radicaux suivants éventuellement substitués: alkyle, alcényle, alcynyle, cycloalkyle, cycloalkylalkyle, aryle, arylalkyle, hétérocyclyle ou hétérocyclylalkyle; les composés 1-méthyl-3-(4-cyano-2-fluorophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluorophényl)-4-bromo-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-nitrophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-éthylsulfonylaminophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-éthoxycarbonylméthoxyphényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-chlorophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-méthylthiophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-aminophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-hydroxyphényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-chlorophényl)-4-chloro-5-difluorométhoxy-pyrazole, 1-méthyl-3-(4-cyano-2-fluoro-5-aminosulfonylphényl)-4-chloro-5-difluorométhoxy-pyrazole et 1-méthyl-3-(4-cyano-2-fluoro-5-fluorosulfonylphényl)-4-chloro-5-difluorométhoxy-pyrazole étant exclus par renonciation. L'invention concerne également un procédé pour la production desdits composés, de nouveaux produits intermédiaires et l'utilisation des 3-cyanoarylpyrazoles comme herbicides.
PCT/EP1997/002580 1996-06-03 1997-05-21 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides WO1997046535A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP10500145A JP2000512275A (ja) 1996-06-03 1997-05-21 ３―シアノアリールピラゾールおよび除草剤としてのそれらの使用
EP97923954A EP0906285A1 (fr) 1996-06-03 1997-05-21 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
BR9709521A BR9709521A (pt) 1996-06-03 1997-05-21 "3-Cianoaril-pirazóis"
CA002256508A CA2256508A1 (fr) 1996-06-03 1997-05-21 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
AU29585/97A AU2958597A (en) 1996-06-03 1997-05-21 3-cyanoaryl pyrazoles and use thereof as herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996122189 DE19622189A1 (de) 1996-06-03 1996-06-03 3-Cyanaryl-pyrazole
DE19622189.7 1996-06-03

Publications (1)

Publication Number Publication Date
WO1997046535A1 true WO1997046535A1 (fr) 1997-12-11

Family

ID=7795979

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002580 WO1997046535A1 (fr) 1996-06-03 1997-05-21 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides

Country Status (8)

Country Link
EP (1) EP0906285A1 (fr)
JP (1) JP2000512275A (fr)
CN (1) CN1227545A (fr)
AU (1) AU2958597A (fr)
BR (1) BR9709521A (fr)
CA (1) CA2256508A1 (fr)
DE (1) DE19622189A1 (fr)
WO (1) WO1997046535A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001106688A (ja) * 1999-08-05 2001-04-17 Isagro Ricerca Srl 除草活性を有するフェニルピラゾール類
US6495492B1 (en) 1998-08-26 2002-12-17 Bayer Aktiengesellschaft Substituted 3-aryl-pyrazoles
US6573219B1 (en) 1999-08-10 2003-06-03 Bayer Aktiengesellschaft Substituted heterocyclyl-2H-chromenes
EP1170377A3 (fr) * 2000-07-05 2004-02-11 Bayer CropScience AG Méthode pour l'identification des inhibiteurs de l'oxydase protoporphyrinogène

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0016787D0 (en) 2000-07-07 2000-08-30 Pfizer Ltd Compounds useful in therapy
JP2004519456A (ja) * 2001-01-16 2004-07-02 ビーエーエスエフ アクチェンゲゼルシャフト １−アルキル−３−アリール−５−ジフルオロメトキシ−１ｈ−ピラゾールの製造方法
CN101870677A (zh) * 2010-06-28 2010-10-27 大连理工大学 一种5-芳甲氧基苯基吡唑类化合物及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2537047A1 (de) * 1975-08-20 1977-03-03 Bayer Ag Vinylthionophosphorsaeureester, verfahren zu ihrer herstellung sowie ihre verwendung als insektizide und akarizide
US4546113A (en) * 1983-04-14 1985-10-08 Pfizer Inc. Antiprotozoal diamidines
EP0279698A2 (fr) * 1987-02-20 1988-08-24 The Wellcome Foundation Limited Composés pesticides
EP0656348A2 (fr) * 1993-12-03 1995-06-07 F. Hoffmann-La Roche Ag Dérivés d'acide acérique comme médicaments
DE4417837A1 (de) * 1994-05-20 1995-11-23 Basf Ag Substituierte 3-Phenylpyrazole
WO1996001255A1 (fr) * 1994-07-01 1996-01-18 Zeneca Limited Derives de 3-(cyanophenyle)-pyrazole utilises comme herbicides
EP0708107A1 (fr) * 1994-10-20 1996-04-24 Shin-Etsu Chemical Co., Ltd. Nouveaux composés de silacyclohexane, une composition de cristaux liquides les comprenant et un dispositif à cristaux liquides contenant ladite composition
WO1996015115A1 (fr) * 1994-11-10 1996-05-23 Zeneca Limited Composes de pyrazole herbicides
WO1997000246A1 (fr) * 1995-06-15 1997-01-03 Novartis Ag Nouveaux herbicides

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2537047A1 (de) * 1975-08-20 1977-03-03 Bayer Ag Vinylthionophosphorsaeureester, verfahren zu ihrer herstellung sowie ihre verwendung als insektizide und akarizide
US4546113A (en) * 1983-04-14 1985-10-08 Pfizer Inc. Antiprotozoal diamidines
EP0279698A2 (fr) * 1987-02-20 1988-08-24 The Wellcome Foundation Limited Composés pesticides
EP0656348A2 (fr) * 1993-12-03 1995-06-07 F. Hoffmann-La Roche Ag Dérivés d'acide acérique comme médicaments
DE4417837A1 (de) * 1994-05-20 1995-11-23 Basf Ag Substituierte 3-Phenylpyrazole
WO1996001255A1 (fr) * 1994-07-01 1996-01-18 Zeneca Limited Derives de 3-(cyanophenyle)-pyrazole utilises comme herbicides
EP0708107A1 (fr) * 1994-10-20 1996-04-24 Shin-Etsu Chemical Co., Ltd. Nouveaux composés de silacyclohexane, une composition de cristaux liquides les comprenant et un dispositif à cristaux liquides contenant ladite composition
WO1996015115A1 (fr) * 1994-11-10 1996-05-23 Zeneca Limited Composes de pyrazole herbicides
WO1997000246A1 (fr) * 1995-06-15 1997-01-03 Novartis Ag Nouveaux herbicides

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ARCH. PHARM., vol. 323, no. 8, 1990, WEINHEIM, DE, pages 507 - 512 *
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 65, no. 6, 1992, TOKYO JP, pages 1741 - 1743 *
CHEMICAL ABSTRACTS, vol. 101, no. 23, 3 December 1984, Columbus, Ohio, US; abstract no. 211111, CAPASSO F ET AL: "1,5-Naphthodiazepine derivatives with potential biological activity" XP002040383 *
DATABASE CROSSFIRE Beilstein Informationssysteme GmbH, Frankfurt, DE; XP002040384 *
DATABASE CROSSFIRE Beilstein Informationssysteme GmbH, Frankfurt, DE; XP002040385 *
REND. ACCAD. SCI. FIS. MAT., NAPLES, vol. 50, no. 2, 1983, pages 247 - 257 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495492B1 (en) 1998-08-26 2002-12-17 Bayer Aktiengesellschaft Substituted 3-aryl-pyrazoles
US6559102B1 (en) 1998-08-26 2003-05-06 Bayer Aktiengesellschaft Substituted 3-aryl-pyrazoles
JP2001106688A (ja) * 1999-08-05 2001-04-17 Isagro Ricerca Srl 除草活性を有するフェニルピラゾール類
US6573219B1 (en) 1999-08-10 2003-06-03 Bayer Aktiengesellschaft Substituted heterocyclyl-2H-chromenes
EP1170377A3 (fr) * 2000-07-05 2004-02-11 Bayer CropScience AG Méthode pour l'identification des inhibiteurs de l'oxydase protoporphyrinogène

Also Published As

Publication number Publication date
JP2000512275A (ja) 2000-09-19
AU2958597A (en) 1998-01-05
BR9709521A (pt) 1999-08-10
DE19622189A1 (de) 1997-12-04
CA2256508A1 (fr) 1997-12-11
EP0906285A1 (fr) 1999-04-07
CN1227545A (zh) 1999-09-01

Similar Documents

Publication Publication Date Title
DE19641692A1 (de) Substituierte 2,4-Diamino-1,3,5-triazine
DE19641691A1 (de) Substituierte 2-Amino-4-alkylamino-1,3,5-triazine
WO1999052878A1 (fr) Pyridazinones de phenyle substituees
WO1997046535A1 (fr) 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
WO1998042684A1 (fr) 2,4-diamino-1,3,5-triazines substituees utilisees comme herbicides
DE19838706A1 (de) Substituierte 3-Aryl-pyrazole
DE19854081A1 (de) Substituierte N-Pyrazolyl-phenoxynicotinsäure-(thio)amide
EP0946544B1 (fr) Heterocyclyluraciles
DE19921883A1 (de) Substituierte Thienocycloalk(en)ylamino-1,3,5-triazine
WO2000043375A2 (fr) Composes heterocycliques d'aryle substitues
WO1997040018A1 (fr) 3-cyanoarylpyrazoles et leur utilisation comme herbicides
WO1998006702A1 (fr) 1-(3-pyrazolyl)-pyrazoles substitues a action herbicide et produits intermediaires pour leur fabrication
WO1998054155A1 (fr) Iminoalcoxy-phenyluraciles substitues, leur fabrication et leur utilisation comme herbicides
EP0956283B1 (fr) Phenyltriazoline(thi)ones substitues et leur utilisation comme herbicides
WO2000008000A1 (fr) Triazinones substituees utilisees comme herbicides
WO1999007698A1 (fr) (hetero)aryloxypyrazoles utilises comme herbicides
DE19728125A1 (de) Substituierte Aryluracile
DE19937500A1 (de) Substituierte Heterocyclylbenzofurane
DE19652426A1 (de) Heterocyclyluracile
DE19649094A1 (de) Phenyl-uracil-Derivate
DE19919790A1 (de) Verwendung von N-substituierten Heterocyclyalkylaminen als Herbizide und neue N-substituierte Thienylaklylamine
WO1999059977A1 (fr) 1,3-diaza-2-(thi)oxo-cycloalcanes substitues
DE19704370A1 (de) Substituierte Benzoxazolyloxyacetanilide
WO1999048886A1 (fr) Aminooxyalcancarboxamides substitues
WO1998040362A1 (fr) Arylalkyluraciles substituees

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 97197015.7

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CN CZ HU IL JP KR KZ LK MX NO NZ PL RO RU SK TR UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997923954

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2256508

Country of ref document: CA

Ref document number: 2256508

Country of ref document: CA

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1997923954

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1997923954

Country of ref document: EP