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WO1997012883A1 - Produits intermediaires et procede de production de derives substitues d'acide salicylique utiles comme agents phytosanitaires - Google Patents

Produits intermediaires et procede de production de derives substitues d'acide salicylique utiles comme agents phytosanitaires Download PDF

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Publication number
WO1997012883A1
WO1997012883A1 PCT/EP1996/004201 EP9604201W WO9712883A1 WO 1997012883 A1 WO1997012883 A1 WO 1997012883A1 EP 9604201 W EP9604201 W EP 9604201W WO 9712883 A1 WO9712883 A1 WO 9712883A1
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formula
alkyl
organic tin
preparation
compounds
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PCT/EP1996/004201
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German (de)
English (en)
Inventor
Joachim Rheinheimer
Uwe Josef Vogelbacher
Ernst Baumann
Ulf Misslitz
Karl-Otto Westphalen
Helmut Walter
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Basf Aktiengesellschaft
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Publication of WO1997012883A1 publication Critical patent/WO1997012883A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • A01N55/04—Tin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen

Definitions

  • the present invention relates to organic tin compounds of the formula I.
  • R 1 optionally substituted benzyl, alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl;
  • R 2 alkyl, cycloalkyl.
  • the above-mentioned compounds serve in particular as intermediates for the production of crop protection agents, e.g. of substituted salicylic acid derivatives.
  • Substituted salicylic acid derivatives with good herbicidal and / or bioregulatory activity are known from EP-A 652 216, EP-A 346 789, WO 93/03017 and EP-A 402 751.
  • the object of the invention was to provide new intermediates for the preparation of substituted salicylic acid derivatives and to provide an advantageous process for the preparation of these compounds.
  • the alkyl group can be represented by one to the maximum possible number
  • the phenyl ring can carry one to five halogen atoms, one to three C 1 -C 4 alkyl or C 4 -C 4 alkoxy groups and / or one to three of the following radicals: nitro, cyano, C ⁇ ⁇ C4 halo-alkyl, C ⁇ -C4-haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ ⁇ C 4 alkylamino, di-C ⁇ -C 4 alkylamino, C ⁇ -C 4 alkylcarbonyl, C ⁇ ⁇ C 4 -Alkoxycarbonyl, phenyl, with one to three halogen atoms or one to three methyl groups substituted phenyl, phenoxy, with one to three halogen atoms or one to three methyl groups substituted phenoxy.
  • -C-C 4 alkyl methyl, ethyl, i-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-propy1, 1, 1-dimethyl-ethyl.
  • C 1 -C 6 -alkyl C 1 -C 4 -alkyl and 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-butyl, 3-methyl-butyl, 2-methyl-2-butyl, 3-methyl- 2-butyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 2,2-dimethyl-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-pentyl, 3-methyl- pentyl, 4-methyl-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2, 2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 3, 3-dimethyl-1-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1, 2,
  • haloalkyl chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl, 2,2,2-trifluoroethyl , 2-chloro-l, 1,2-trifluoroethyl and pentafluoroethyl, decafluorobutyl, 1,1-bis-trifluoromethyl-2,2,2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, trichloromethyl and chlorodifluoromethyl.
  • C 3 -C 8 cycloalkyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, particularly preferably cyclopropyl, cyclopentyl and cyclohexyl.
  • C 1 -C 4 -alkylcarbonyl acetyl, propionyl, 1-propylcarbonyl, 2-propylcarbonyl, 1-butylcarbonyl, 2-butylcarbony1, 2-methylpropylcarbonyl, 1, 1-dimethy1-ethylcarbonyl.
  • C ⁇ -C 4 alkoxycarbonyl ethoxycarbonyl, propoxycarbonyl, 1-propyloxycarbonyl, 2-propyloxycarbonyl, 1-butyloxycarbonyl, 2-butyloxycarbonyl, 2-methyl-propyloxycarbonyl, 1, 1-dimethy1-ethoxycarbonyl.
  • C 1 -C 4 alkoxy methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 2-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, especially methoxy, ethoxy, 1-methylethoxy.
  • Ci-C ⁇ -alkoxy -C-C 4 alkoxy and pentoxy, 2-pentoxy, 3-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl1-2-butoxy, 3-methyl-2-butoxy , 1, 1-Dimethy1-propoxy, 1,2-dimethyl-propoxy, 2,2-dimethyl-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4th -Methyl-pentoxy, 2-methyl-2-pentoxy, 3-methyl-1-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl -butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3-dimethy1-2-butoxy, 3, 3-dimethyl-2-butoxy, especially methoxy, ethoxy, 1-methylethoxy.
  • C 1 -C 4 haloalkoxy difluoromethoxy, trifluoromethoxy, chloro-difluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1, 1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chlorine -l, 1,2-trifluoroethoxy and pentafluoroethoxy, 1, 1,2, 3, 3, 3-hexafluoropropoxy, heptafluoropropoxy, decafluorobutoxy, 1, 1-bis-trifluoromethyl-2,2,2-trifluoroethoxy , preferably difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy.
  • C 3 -C ⁇ 2 -cycloalkoxy cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy and cyclododecyloxy, particularly preferably cyclopropoxy, cyclopentoxy and cyclohexyloxy.
  • C ⁇ -C 4 -Alkylcarbonyloxy acetoxy, propionyloxy, 1-propylcarbony1-oxy, 2-propylcarbonyloxy, 1-butylcarbonyloxy, 2-butylcarbonyloxy, 2-methyl-propylcarbonyloxy, 1,1-dimethyl-ethylcarbonyloxy.
  • C 1 -C 4 -Alkylthio methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 2-butylthio, 1-methyl-propylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, especially methylthio, ethylthio, 1- Methyl ethylthio.
  • C 1 -C 4 alkylsulfonyl methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 2-butylisulfonyl, 1-methylisulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methyl
  • Di-C ⁇ -C 4 alkylamino dimethylamino, N-methyl-N-ethylamino, diethylamino, N-methyl-N-propylamino, N-Ethy1-N-propylamino, dipropylamino, diisopropylamino, N-isopropyl-N-methylamino, N -Ethy1-N-isopropylamino, N-isopropyl-N-propylamino, dibutylamino, di-2-methylpropylamino, di-1-methylpropylamino, N-butyl-N-methylamino and isomers, N-butyl-N-ethylamino and isomers , N-butyl-N-propylamino and isomers.
  • R 1 optionally substituted benzyl, C 1 -C 6 -alkyl, dihydro pyranyl, tri-C 6 -alkylsilyl, C 4 -alkoxy-C 4 -alkyl and di-C 4 -alkoxy-C 1 -C C 4 alkyl;
  • R 2 Ci-Ce alkyl, C 3 -C 6 cycloalkyl.
  • organic tin compounds of the formula I are prepared by metalating the underlying benzoic acid with a suitable base at low temperatures and then reacting it with a trialkyltin compound of the formula III to give the tin compound I:
  • Cycloalkyl or alkyl-lithium compounds are particularly suitable as bases, and the commercially available isomers of butyl and hexyllithium are particularly suitable. It is often expedient to add an auxiliary to promote the metallization. For this purpose ethers, alcoholates such as potassium tert-butoxide or amines such as tetramethylethylenediamine are suitable. The metalation can take place at temperatures from 0 to 130 ° C., preferably between -50 and -100 ° C.
  • reaction times for the metalation can range from a few minutes to a few hours.
  • the trialkyltin compound is then added, where X is the usual leaving groups, preferably chlorine or bromine. The above applies to the temperature during the addition and the subsequent reaction time.
  • An aqueous or non-aqueous workup can then be carried out, it being useful in the first case to keep the pH of the aqueous phase constant with a buffer.
  • the organic tin compounds of the formula I can be further purified, for example by chromatography on silica gel. They also prove to be stable against water at various pH values during processing and can be stored at room temperature.
  • the organic tin compounds of formula I have biocidal properties.
  • the herbicidal properties are particularly pronounced.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and harmful grasses without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Fogging, dusting, scattering or pouring can be used.
  • the application forms depend on the uses; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. Amines such as N-methylpyrrolidone or water.
  • Paraffin Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol
  • ketones such as cyclohex
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, Metz, adhesive, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surface-active substances are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts sulfated hexa-, hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl, phenyl or nonyl phenyl Tributy
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied within a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably between 0.01 to 95% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • Dissolved mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 mol ethylene oxide with 1 mol castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
  • Wettol ® EM31 non-ionic emulsifier based on ethoxylated castor oil. A stable emulsion concentrate is obtained.
  • substituted salicylic acid derivatives I can be used with numerous representatives of other herbicidal or growth-regulating groups of active ingredients are mixed and applied together.
  • 1,2, 4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazione come as mixing partners , 2-aroyl-l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and their derivatives , Dihydrobenz
  • the amount of active ingredient applied is 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance depending on the control target, the season, the target plants and the growth stage.
  • Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
  • the vessels were sprinkled lightly to encourage germination and growth, and then clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants are either sown directly and grown in the same containers or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment is 3.0 kg / ha a.S.
  • the plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • R 3 is chlorine, bromine, iodine, fluorosulfonyl or fluoroalkyl sulfonyl;
  • A is a 5-membered heteroaromatic linked via a carbon atom and having an oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one or two nitrogen atoms and additionally a sulfur or oxygen atom in the ring, which may be substituted one or more times can be; a 6-membered heteroaromatic with one to four nitrogen atoms in the ring, which can optionally be substituted one or more times; optionally mono- or polysubstituted phenyl
  • heterocycles are particularly preferred as 5-membered heteroaromatics: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl , 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-0xazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4 -Isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2, 3-triazol-l-yl, 1,2,3-triazol-4-yl, l, 2,3-triazole -5-yl, (IH) 1,2,4-triazol-
  • heterocycles are particularly preferred as ⁇ -membered heteroaromatics: 2-pyridyl, 4-pyridyl, 3-pyridyl, 2 7 pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4 -yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6 -yl, l, 2,4,5-tetrazin-3-yl.
  • substituents fluorine, chlorine, bromine, iodine, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfoxy, optionally substituted C 3 -C 6 cycloalkyl, C 3 -Ce -Cycloalkoxy, cyano, nitro, formyl, -C-C 4 -alkoxycarbonyl, Di-C ⁇ -C 4 -alkylamino, C ⁇ ⁇ C 4 - alkylamino.
  • a catalytically active palladium compound is used in this process. Any palladium salts or complexes which are at least partially soluble in the reaction mixture are suitable.
  • the oxidation state of the palladium can be 0 or 2.
  • the following counterions are suitable for the palladium salts: chloride, bromide, iodide, sulfate, acetate, trifluoroacetate, acetylacetonate or hexafluoro-2,4-pentadionate.
  • Many different palladium complexes can be used. The only requirement is that the ligands on the palladium can be displaced from the substrate under the reaction conditions.
  • Phosphine ligands such as aryl-alkyl phosphines such as methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as triphenylphosphine, tritolyl- phosphine, trixylylphosphine, trihetarylphosphines such as trifurylphosphine or dimeric phosphines.
  • Olefinic ligands such as, inter alia, dibenzylidene acetone or its salts, cycloocta-1,5-diene or amines such as trialkylamines (for example triethylamine, tetramethylethylene diamine, N-methylmorpholine) or pyridine are also very suitable.
  • the complex used can be used directly in the reaction. So you can e.g. with tetrakistriphenylphosphine palladium (O), bistriphenylphosphine palladium dichloride, bistriphenylphosphine palladium diacetate, a dibenzylideneacetone palladium (O) complex, tetrakismethyldiphenylphosphine palladium (O) or bis (1,2-diphenylphosphino dichloride) palladium dichloride.
  • a palladium salt and additionally a suitable ligand can also be used, which then only form the catalytically active complex in situ. This procedure is available e.g.
  • phosphine ligands such as e.g. Trifuryl phosphine or tritolyl phosphine.
  • Palladium complexes such as e.g. Tris (dibenzylidene acetone) dipalladium, bis (dibenzylidene acetone) palladium or 1,5-cyclooctadiene palladium dichloride by the addition of ligands such as e.g. Trifurylphosphine or Tritolyl ⁇ phosphine can be activated further.
  • the palladium compound (salt or complex), based on the compound I is used. Higher quantities are possible but rather uneconomical.
  • the amount of V, based on the starting material I is generally from 0.8 to 3, preferably from 0.95 to 1.5, molar equivalents. All solvents which do not themselves react with the substrates used are suitable for the reaction. Polar solvents accelerate the reaction.
  • Ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or amines such as triethylamine are particularly suitable.
  • amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or amines such as triethylamine are particularly suitable.
  • the use of mixtures, for example of ethers with amides, is often advantageous.
  • Alkyl alcohols and water can also be considered as mixing partners, especially if the radical B contains a boron atom.
  • tetraalkylammonium halides or alkali metal halides such as lithium chloride is often helpful and is particularly advisable if Z stands for a sulfonyloxy radical.
  • the radical B contains a boron atom, it is often useful to add an organic or inorganic base such as potassium carbonate, sodium carbonate, calcium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, potassium phosphate, sodium phosphate, pyridine or an amine such as triethylamine.
  • the reaction temperature is between -20 and 200 ° C, preferably between 50 and 160 ° C.
  • the reaction times are usually between a few minutes and 50 hours, usually 0.5 to 10 hours.
  • low-boiling solvents it is sometimes useful to carry out the reaction under autogenous pressure in the autoclave.
  • the invention furthermore comprises, as intermediates, the substituted salicylic acid derivatives of the formula IV
  • substituents R 1 and A have the meaning described above, with the proviso that the radical A is not optionally substituted phenyl.
  • the preferred substituents are also the same as those described above.
  • the compounds of formula IV serve as intermediates in the synthesis of new and known heterocyclically substituted salicylic acid derivatives, the herbicidal activity of which is reported, for example, in the patent applications cited above.
  • the radical R 1 is first removed using known methods such as hydrolysis or hydrogenolysis in order to release the hydroxyl group.
  • the heterocyclically substituted salicylic acids which are easily accessible in this way, can then be reacted by known processes, for example with a suitable pyrimidine derivative, to give the desired crop protection active compounds.
  • 2-methoxy-6-trimethylstannylbenzoic acid can be obtained analogously to the example above if chlorotrimethylstannane is used instead of chlortributylstannane.
  • 2-Methoxy-6- (5-trifluoromethylpyridin-2-yl) benzoic acid (No. 1,429) can be prepared largely analogously to 2-methoxy-6- (2-fluoropyridin-5-yl) benzoic acid: Yield (after Cleaning) 47%.
  • i H-NMR (DMSO-de): ⁇ 3.81 (s); 7.24 (d); 7.33 (d); 7.51 (t); 7.87 (d); 8.29 (d); 8.97 (s); 12.80 (widened).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

Composés organiques d'étain de formule (I), dans laquelle les restes ont la notation suivante: R1 désigne benzyle, alkyle, dihydropyranyle, trialkylsilyle, alkoxyalkyle et dialkoxyalkyle le cas échéant substitués; et R2 désigne alkyle ou cycloalkyle. L'invention concerne également leur procédé de préparation, un agent biocide et leur utilisation comme agents biocides.
PCT/EP1996/004201 1995-10-02 1996-09-26 Produits intermediaires et procede de production de derives substitues d'acide salicylique utiles comme agents phytosanitaires WO1997012883A1 (fr)

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DE19536811A DE19536811A1 (de) 1995-10-02 1995-10-02 Zwischenprodukte und Verfahren zur Herstellung von substituierten Salicylsäurederivaten als Pflanzenschutzmittel
DE19536811.8 1995-10-02

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WO1999021837A1 (fr) * 1997-10-27 1999-05-06 Isk Americas Incorporated Composes benzeniques substitues, technique de production et compositions herbicides et defoliantes contenant ces composes
WO2002014276A1 (fr) * 2000-08-10 2002-02-21 Tanabe Seiyaku Co., Ltd. Composes a base de benzoylaminoisoindoline, leurs procedes de preparation et produits intermediaires utilises dans leur synthese
US8263630B2 (en) 2008-02-12 2012-09-11 Bristol-Myers Squibb Company 1,2,3-triazoles as 11-beta hydroxysteroid dehydrogenase type I inhibitors
US10220027B2 (en) 2011-07-13 2019-03-05 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US10329286B2 (en) 2016-06-13 2019-06-25 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10421730B2 (en) 2016-06-13 2019-09-24 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11225473B2 (en) 2019-01-15 2022-01-18 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11524005B2 (en) 2019-02-19 2022-12-13 Gilead Sciences, Inc. Solid forms of FXR agonists
US11833150B2 (en) 2017-03-28 2023-12-05 Gilead Sciences, Inc. Methods of treating liver disease

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CA2950084C (fr) 2014-06-06 2022-04-19 Basf Se Utilisation d'oxadiazoles substitues pour lutter contre des fongus phytopathogenes
US10227303B2 (en) * 2015-05-05 2019-03-12 Srf Limited Process for the preparation of halosubstituted trifluoromethylpyridines
WO2017081309A1 (fr) 2015-11-13 2017-05-18 Basf Se Oxadiazoles substitués pour lutter contre des champignons phytopathogènes
AR106679A1 (es) 2015-11-13 2018-02-07 Basf Se Oxadiazoles sustituidos para combatir hongos fitopatógenos
US10674727B2 (en) 2015-11-19 2020-06-09 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018069897B1 (pt) 2016-04-11 2023-01-17 Basf Se Composto de fórmula i, composição agroquímica, processo para a preparação de compostos de fórmula i, uso não terapêutico de compostos e método para o combate de fungos fitopatogênicos nocivos

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EP0402751A1 (fr) * 1989-06-14 1990-12-19 BASF Aktiengesellschaft Dérivés d'aldéhyde salicylique et d'acide salicylique et leurs analogues à base de soufre, procédés pour leur préparation et leur utilisation comme herbicides et biorégulateurs
DE4337323A1 (de) * 1993-11-02 1995-05-04 Basf Ag Substituierte Pyridylsalicylaldehyd- bzw. salicylsäurederivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide

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EP0402751A1 (fr) * 1989-06-14 1990-12-19 BASF Aktiengesellschaft Dérivés d'aldéhyde salicylique et d'acide salicylique et leurs analogues à base de soufre, procédés pour leur préparation et leur utilisation comme herbicides et biorégulateurs
DE4337323A1 (de) * 1993-11-02 1995-05-04 Basf Ag Substituierte Pyridylsalicylaldehyd- bzw. salicylsäurederivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide
EP0652216A2 (fr) * 1993-11-02 1995-05-10 BASF Aktiengesellschaft Dérivés d'aldéhyde salicylique et d'acide salicylique de pyridine, procédés pour leur préparation et leur utilisation comme herbicides

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999021837A1 (fr) * 1997-10-27 1999-05-06 Isk Americas Incorporated Composes benzeniques substitues, technique de production et compositions herbicides et defoliantes contenant ces composes
US6355799B1 (en) 1997-10-27 2002-03-12 Isk Americas Incorporated Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them
US6545161B2 (en) 1997-10-27 2003-04-08 Isk Americas Incorporated Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them
USRE39590E1 (en) * 1997-10-27 2007-04-24 Isk Americas Incorporated Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them
WO2002014276A1 (fr) * 2000-08-10 2002-02-21 Tanabe Seiyaku Co., Ltd. Composes a base de benzoylaminoisoindoline, leurs procedes de preparation et produits intermediaires utilises dans leur synthese
US8263630B2 (en) 2008-02-12 2012-09-11 Bristol-Myers Squibb Company 1,2,3-triazoles as 11-beta hydroxysteroid dehydrogenase type I inhibitors
US10220027B2 (en) 2011-07-13 2019-03-05 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US10485795B2 (en) 2011-07-13 2019-11-26 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US10421730B2 (en) 2016-06-13 2019-09-24 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10329286B2 (en) 2016-06-13 2019-06-25 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10774054B2 (en) 2016-06-13 2020-09-15 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10981881B2 (en) 2016-06-13 2021-04-20 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11247986B2 (en) 2016-06-13 2022-02-15 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11739065B2 (en) 2016-06-13 2023-08-29 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11833150B2 (en) 2017-03-28 2023-12-05 Gilead Sciences, Inc. Methods of treating liver disease
US11225473B2 (en) 2019-01-15 2022-01-18 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11524005B2 (en) 2019-02-19 2022-12-13 Gilead Sciences, Inc. Solid forms of FXR agonists
US12102625B2 (en) 2019-02-19 2024-10-01 Gilead Sciences, Inc. Solid forms of FXR agonists

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