Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C261/00—Derivatives of cyanic acid
  • C07C261/04—Cyanamides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
  • C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
  • C07D333/66—Nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
  • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
  • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

• the invention relates to new substituted N-cyano-amidines, a process for their preparation and their use as herbicides.
• R 1 stands for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl and
• the general formula (I) includes the possible E and Z configuration isomers.
• the hydrocarbon chains such as alkyl, alkenyl or alkynyl, are each straight-chain or branched.
• R 1 preferably represents hydrogen, optionally substituted by cyano, halogen, dC 4 -alkoxy, C 1 -C 4 -alkylthio, Q-alkylsulfinyl or C 1 -C 4 -alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms, for each counter- appropriate, halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen or C ⁇ -C 4 - substituted alkyl cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, in each case optionally substituted by nitro, cyano, halo, C ⁇ -C 4 - alkyl, C ⁇ -C4-haloalkyl, C ⁇ -C
• aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl part.
• R preferably stands for benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl from the list below
• C ⁇ -C alkylamino di- (C ⁇ -C4 alkyl) amino, C ⁇ -C alkyl-carbonyl, Cj-C 4 - alkoxy-carbonyl, C i -C 4 - alkylamino-carbonyl, di- (C i -C 4 alkyl) amino carbonyl, C ⁇ -C4 alkyl-carbonyl-amino, C ⁇ -C 4 -alkoxy-carbonyl-amino, - C 4 -alkyl-amino-carbonyl-amino, Ci-C4 Alkyl sulfonyl amino.
• ⁇ is particularly preferably hydrogen, each optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propy - Isulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine, chlorine or bromine Ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, for cyclopropyl, cyclobutyl,
• R> 2 particularly preferably represents one of the cyclic and heterocychic groupings mentioned above, the substituents being selected from one of the groupings listed below:
• Butyroylamino methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino.
• R 1 very particularly preferably represents hydrogen and in each case methyl, ethyl, n- or i substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfmyl, methylsulfonyl, ethylsulfonyl -Propyl.
• R very particularly preferably represents benzo-fused cycloalk (en) yl from the list below
• R 1 most preferably represents hydrogen, methyl, ethyl or n- or i-propyl.
• R 2 most preferably represents one of the following groups:
• radicals listed above or those specified in preferred ranges 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.
• the new substituted N-cyanoamidines of the general formula (I) have interesting biological properties. They are particularly characterized by their strong herbicidal activity.
• R ' represents alkyl
• Formula (II) provides a general definition of the N-cyanoimidic acid esters to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I).
• R 1 preferably has the meaning which has already been given above as preferred, particularly preferred, very particularly preferred or most preferred for R 1 in connection with the description of the compounds of the general formula (I) according to the invention has been;
• R ' preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
• the N-cyano-imidic acid esters of the general formula (II) are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 104 (1982), 235-239; loc. Cit.
• Formula (III) provides a general definition of the amino compounds to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I).
• R 2 preferably has the meaning which has already been given above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred, very particularly preferred or most preferred for R 2 .
• amino compounds of the general formula (III) are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 88 (1966), 2233-2240; loc. Cit. 95 (1973), 4083-4084); J. Chem. Soc. C 1966, 717-722; Synthesis 1980, 695-697; Tetrahedron 24: 3681-3696 (1968); loc. cit. 50 (1994), 3627-3638).
• the process according to the invention for the preparation of compounds of the general formula (I) is optionally carried out using a reaction auxiliary.
• the usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or alkanolates, such as, for example, sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, Sodium or potassium methoxide, ethanolate, n or i propanolate, n, i, s or t butanolate; also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine,
• Ethyl-2-methyl-pyridine 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3, 0] -non-5-ene (DBN), or 1,8-diazabicyclo [5, 4.0] -undec-7-ene (DBU).
• DABCO 1,4-diazabicyclo [2,2,2] octane
• DBN 1,5-diazabicyclo [4,3, 0] -non-5-ene
• DBU 1,8-diazabicyclo [5, 4.0] -undec-7-ene
• reaction aids can be dispensed with.
• the process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent.
• a diluent In addition to water, the main diluents are inert organic ones
• Solvent 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; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters
• reaction temperatures can be carried out when carrying out the process according to the invention.
• Process can be varied over a wide range. Generally you work at temperatures between 0 ° C and 150 ° C, preferably between 10 ° 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 elevated or reduced pressure - generally between 0.1 bar and 10 bar.
• the starting materials are generally used in approximately equimolar 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, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. 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 all plants that grow 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 e.g. can be used in the following plants:
• the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on
• the active compounds according to the invention for weed control in permanent crops e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture areas as well for selective weed control in annual crops.
• the compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for selective use Control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre- and post-emergence.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
• formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using 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 such as calcite,
• Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
• 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, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95 percent by weight
• Active ingredient 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.
• Flufenacet Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet-sulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Fluprop-acil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-flurene), , Fluroxypyr (- methyl), Flu ⁇ rimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropylammonium), Halosafen, Haloxyfop-
• Tebutam Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamamide, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tiocarb-azil, Tralkoxydim, Triallate, Triasul ariseon, Tribenuroni-, Tribenuron (-di- Trifluralin and triflusulfuron.
• a mixture with other known active compounds such as fungicides, insecticides, acaricides, 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 in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
• the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
• the amount of active ingredient used can vary over a wide range. It essentially depends 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.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
• Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area.
• the concentration of the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.
• the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
• Example B the compound according to Preparation Example 1 shows a strong action against weeds.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
• Test plants with a height of 5 - 15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
• the concentration of the spray liquor is chosen so that in
• the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
• the compound according to Preparation Example 1 shows a strong action against weeds.

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

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• 1999
  • 1999-05-12 DE DE19921886A patent/DE19921886A1/de not_active Withdrawn
• 2000
  • 2000-05-04 CN CN00807457A patent/CN1350517A/zh active Pending
  • 2000-05-04 WO PCT/EP2000/004013 patent/WO2000069813A1/de not_active Application Discontinuation
  • 2000-05-04 CA CA002373429A patent/CA2373429A1/en not_active Abandoned
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• 2002
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