Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • 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
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
  • C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/12—Oxygen or sulfur atoms

Definitions

• the invention relates to new arylalkyl compounds, processes for their preparation, new intermediates and their use as herbicides.
• n the numbers 0 to 5
• n stands for the numbers 0 to 4,
• Q represents O, S, SO or SO 2 ,
• R 1 represents hydrogen or optionally substituted alkyl
• R 2 represents hydrogen or optionally substituted alkyl
• R 3 represents hydrogen, cyano, formyl, or a radical of the series which is optionally substituted by cyano, halogen or alkoxy
• alkyl alkylcarbonyl, alkoxycarbonyl, alkenyl or alkynyl,
• R 4 represents hydrogen, cyano, formyl, or a radical of the series alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkynyl which is optionally substituted by cyano, halogen or alkoxy,
• R 5 represents hydrogen, cyano, formyl, or a radical of the series alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkynyl which is optionally substituted by cyano, halogen or alkoxy,
• R 6 represents hydrogen, cyano, formyl, or a radical of the series alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkynyl which is optionally substituted by cyano, halogen or alkoxy,
• R 7 represents hydrogen, amino, cyano, formyl, or a radical of the series alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkenyl, alkynyl or cycloalkyl which is optionally substituted by cyano, halogen or alkoxy, and
• R 8 for hydrogen, halogen, or for each optionally by
• R represents alkyl
• X 1 represents halogen
• X 2 represents halogen
• n, Y and Z have the meanings given above and
• Q 1 represents oxygen or sulfur, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and if appropriate subsequently then carries out electrophilic or nucleophilic substitution reactions in the usual manner as part of the definition of substituents
• the compounds of the general formula (I) can also be converted into other compounds of the general formula (I) according to the above by further customary methods
• Definition can be converted, for example by conventional conversions of carboxylic acid groups or their derivatives (e.g. X: COOH -> COOCH3, COOCH3 ⁇ CONH 2 , CONH 2 ⁇ CN, CN ⁇ CSNH 2 ), by alkylation reactions (e.g. R 3 , R 4 , R 5 , R 6 'H ⁇ CH3 or CHF2) or by oxidation (eg BQS - »SO or SO 2 ) - see also the manufacturing examples.
• carboxylic acid groups or their derivatives e.g. X: COOH -> COOCH3, COOCH3 ⁇ CONH 2 , CONH 2 ⁇ CN, CN ⁇ CSNH 2
• alkylation reactions e.g. R 3 , R 4 , R 5 , R 6 'H ⁇ CH3 or CHF2
• oxidation eg BQS - »SO or SO 2
• the new substituted arylalkyl compounds of the general formula (I) are notable for strong herbicidal activity
• saturated or unsaturated hydrocarbon chains 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) in which
• n the numbers 0 to 4
• n the numbers 0 to 3
• Q represents O, S, SO or SO 2 ,
• R 1 represents hydrogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by halogen
• R 2 represents hydrogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by halogen
• X for hydroxy, mercapto, amino, hydroxyamino, nitro, formyl, carboxy, cyano, carbamoyl, thiocarbamoyl, halogen, or for a radical of the series alkyl, alkoxy, alkylthio which is optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy , Alkylsulfmyl, alkylsulfonyl, alkylamino, di alkylamino, alkylcarbonyl or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl groups,
• Y for nitro, carboxy, cyano, carbamoyl, thiocarbamoyl, halogen, or for a radical of the series alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 6 carbon atoms each optionally substituted by cyano, halogen or C -C-alkoxy is in the alkyl groups, and
• R 3 represents hydrogen, cyano, formyl, or a radical of the series alkyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by cyano, halogen or C1-C4alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or each optionally substituted by halogen Is alkenyl or alkynyl each having 2 to 6 carbon atoms,
• R 4 for hydrogen, cyano, formyl, or for a radical which is optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy
• R 5 for hydrogen, cyano, formyl, or for a radical of the series alkyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for each optionally substituted by halogen Is alkenyl or alkynyl each having 2 to 6 carbon atoms
• R 6 for hydrogen, cyano, formyl, or for a radical optionally substituted by cyano, halogen or C1-C4-alkoxy
• R 7 for hydrogen, amino, cyano, formyl, or for a radical of the series alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl, each with 1 to 6 carbon atoms in each case optionally substituted by cyano, halogen or C -C-alkoxy the alkyl groups, or represents in each case optionally substituted by halogen alkenyl or alkynyl each having 2 to 6 carbon atoms, or represents optionally substituted by cyano or halogen cycloalkyl having 3 to 6 carbon atoms, and
• R 8 for hydrogen, halogen, or for each optionally by
• the invention relates in particular to compounds of the formula (I) in which
• n 0, 1, 2 or 3
• n the numbers 0, 1 or 2
• Q represents O, S, SO or SO 2 ,
• R 1 represents hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine
• R 2 represents hydrogen or methyl, ethyl, n- or i-propyl, n- or i-butyl which is optionally substituted by fluorine and / or chlorine
• X for hydroxy, mercapto, amino, hydroxyamino, nitro, formyl, carboxy, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or for any substituted by cyano, fluorine, chlorine, methoxy or ethoxy
• Y for nitro, carboxy, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, n-, i-, n-, i-, optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,
• R 3 for hydrogen, cyano, formyl, or for each optionally by
• R 4 represents hydrogen, cyano, formyl, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Propionyl, Methoxycarbonyl or ethoxycarbonyl, or represents propenyl, butenyl, propynyl or butynyl which is optionally substituted by fluorine, chlorine or bromine,
• R 5 for hydrogen, cyano, formyl, or for each optionally by
• R 6 for hydrogen, cyano, formyl, or for each optionally by
• R 7 represents hydrogen, amino, cyano, formyl, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino,
• R 8 represents hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethyl
• radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
• Formula (II) provides a general definition of the 4-aryl-semicarbazides to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).
• m, n, Q, R 1 , R 2 , R 3 , R 4 , X and Y preferably or in particular have those meanings which have already been mentioned above in
• R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
• R, R 4 and R 5 have the meanings given above,
• a diluent such as toluene
• aminoarenes of the general formula (VIII) required as precursors are known and / or can be prepared by known processes (cf. US Pat. No. 5,399,543).
• Formula (I) to be used as starting materials 1 - aryl-semicarbazides are generally defined by the formula (III)
• m, n, Q, R 1 , R 2 , R 5 , R 6 , X have and Y preferably or in particular those meanings which have 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 m, n, Q, R 1 , R 2 , R 5 , R 6 , X and Y have been specified
• R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl
• R 5 has the meaning given above
• a diluent such as, for example, toluene or chlorobenzene
• a basic reaction auxiliary such as, for example, sodium or potassium hydride, potassium t-butoxide, triethylamine or ethyldiisopropylamine, at temperatures between 10 ° C. and 150 ° C implements
• a diluent such as, for example, toluene or chlorobenzene
• a basic reaction auxiliary such as, for example, sodium or potassium hydride, potassium t-butoxide, triethylamine or ethyldiisopropylamine
• the isocyanates of the general formula (XI) which are also required as precursors are known synthetic chemicals.
• haloarenes to be used as starting materials in the process (c) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (IV).
• m, n, Q, R 1 , R 2 , X and Y preferably or in particular those meanings which have already been given above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for m, n, Q, R 1 , R 2 , X and Y, X 1 preferably represents fluorine, chlorine or bromine, in particular fluorine or chlorine
• the starting materials of the formula (IV) are known and / or can be prepared by known processes (cf. DE 2526358, US 4249934, US 5262390, WO
• heterocyclic compounds to be used further as starting materials in process (c) according to the invention are generally defined by the formula (V).
• Z preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds according to the invention of formula (I) preferably or as particularly preferred for Z was specified
• the starting materials of the general formula (V) are known and / or can be prepared by known processes (cf. J Org Chem 56 (1991), 5643-5651, DE 4416868).
• the arylalkyl halides to be used as starting materials in the process (d) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (VI).
• m, R 1 , R 2 and X preferably or in particular have those Meanings which have already been given above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for m, R 1 , R 2 and X, X 2 preferably represents chlorine, bromine or iodine, in particular chlorine or bromine
• the starting materials of the general formula (VI) are known synthetic chemicals
• N, Y and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the inventive Compounds of formula (I) preferably or as particularly preferred for n, Y and Z have been indicated, Q 1 preferably represents O or S, in particular O.
• Suitable reaction auxiliaries for processes (a) to (d) according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates and hydrides , hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate,
• DBU Diazabicyclo [5,4,0] -undec-7-ene
• Suitable diluents for carrying out processes (a) to (d) according to the invention are, above all, inert organic solvents. These 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, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone, butanone or methyl isobutyl ketone nitrile or butyronitrile, amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamide, esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol mono
• reaction temperatures can be varied within a substantial range when carrying out processes (a) to (d) according to the invention. In general, temperatures between -20 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
• Processes (a) to (d) according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated 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 in the presence of a reaction auxiliary and the reaction mixture is carried out in all - Agitated several hours at the required temperature. Working up is carried out according to customary methods (see the production examples)
• the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in the broadest sense are understood to mean all plants which grow up in places where they are undesirable, whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used
• 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 rail tracks 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, berry fruit and hop plants are used 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 crops, such as, for example, maize and wheat, both pre-emergence and 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, natural and synthetic substances impregnated with active substances, and very fine encapsulations in polymeric substances
• These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents
• organic substances can also be used.
• Liquid solvents are essentially aromatics, such as xylene, toluene, or alkyl naphthalene, chlorinated aromatics and chlorinated ahphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, ahphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions , mineral and vegetable
• Solid carrier materials that come into question are, for example, ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmole lumps or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, and solid carrier materials for granules Question e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust,
• coconut shells, corn cobs and tobacco stalks as emulsifiers and / or foam-generating agents are suitable, for example, ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates - Hydrolysates, as dispersants are, for example, lignin sulfite and
• Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalene and lecithins and synthetic phosphides, can be used in the formulations. Further additives can be mineral and vegetable oils his
• Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes
• Substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are 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 also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
• Met.zthiazuron Metobenzuron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Napro-anilide, Napropamide, Neburon, Nicosulfuron, Norflurazon Orbencarb, Oryzalin, Oxyzalin, Oxyzalin , Pretilachlor, primisulfuron (-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamides, prosulfocarb, prosulfuron, pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyributicarb, pyridates, pyrithiobac (-sodium), quinine, quinine, quinine Quizalofop (-ethyl), Quizalofop (-p-tefuryl),
• Insecticides Insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible
• the active compounds can be used as such, in the form of their formulations or in 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, spraying, Scatter.
• the active compounds according to the invention can be applied both before and after the plants emerge. They can also be incorporated into the soil before sowing
• the amount of active ingredient used can vary over a wide 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
• Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is 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 boil is chosen so that the desired amounts of active compound are found in 1,000 l of water / ha be 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 desired amounts of active compound are applied in 1000 l of water / ha
• the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
• Cultivated plants such as wheat (10%), strong action against weeds such as Abutilon (100%), Amaranthus (100%), Datura (100%), Solanum (100%), Xanthium (100%) and Setaria (95% )

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)
• Plural Heterocyclic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=7818219

Family Applications (1)

Country Status (10)

Family Cites Families (8)

• 1997
  • 1997-01-24 DE DE19702435A patent/DE19702435A1/de not_active Withdrawn
• 1998
  • 1998-01-10 BR BR9807509A patent/BR9807509A/pt not_active IP Right Cessation
  • 1998-01-10 CN CN98801997A patent/CN1244195A/zh active Pending
  • 1998-01-10 US US09/341,765 patent/US6200935B1/en not_active Expired - Fee Related
  • 1998-01-10 CA CA002278673A patent/CA2278673A1/en not_active Abandoned
  • 1998-01-10 JP JP53152898A patent/JP2001509794A/ja active Pending
  • 1998-01-10 KR KR1019997006015A patent/KR20000069840A/ko not_active Application Discontinuation
  • 1998-01-10 WO PCT/EP1998/000109 patent/WO1998032745A1/de not_active Application Discontinuation
  • 1998-01-10 AU AU62923/98A patent/AU723070B2/en not_active Ceased
  • 1998-01-10 EP EP98906866A patent/EP0968195A1/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events