EP0000002B1 - Tetrahydrofurane derivatives, processes for their preparation and their use as herbicides - Google Patents

Tetrahydrofurane derivatives, processes for their preparation and their use as herbicides Download PDF

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Publication number
EP0000002B1
EP0000002B1 EP78100007A EP78100007A EP0000002B1 EP 0000002 B1 EP0000002 B1 EP 0000002B1 EP 78100007 A EP78100007 A EP 78100007A EP 78100007 A EP78100007 A EP 78100007A EP 0000002 B1 EP0000002 B1 EP 0000002B1
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Prior art keywords
tetrahydrofuran
atoms
alkyl
phenyl
formula
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German (de)
French (fr)
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EP0000002A1 (en
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Thomas Dr. Schmidt
Wilfried Dr. Draber
Ludwig Dr. Eue
Robert Rudolf Dr. Schmidt
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D1/00—Non-positive-displacement machines or engines, e.g. steam turbines

Definitions

  • the invention relates to tetrahydrofuran derivatives, several processes for their preparation and their use as herbicides, in particular as selective herbicides.
  • chloroacetanilides such as, for example, 2-ethyl-6-methyl-N- (1'-methyl-2'-methoxyethyl) chloroacetanilide
  • grass-like weeds cf. DE-A-2 328 340.
  • selectivity of these compounds is not always satisfactory.
  • tetrahydrofuran derivatives have strong herbicidal, in particular selective herbicidal properties.
  • the tetrahydrofuran derivatives according to the invention are superior to the known herbicides, such as, for example, 2-ethyl-6-methyl-N - (1'-methyl-2'-methoxyethyl) -chloroacetanilide, in their herbicidal action and also show a markedly better selectivity important kulfur plants.
  • the active compounds according to the invention thus represent a significant enrichment of herbicides, especially grass herbicides.
  • the alcoholates of the formula II are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyltetrahydrofuran derivatives with suitable strong bases, such as, for example, alkali or alkaline earth amides, hydrides or hydroxides, in an inert solvent.
  • suitable strong bases such as, for example, alkali or alkaline earth amides, hydrides or hydroxides.
  • suitable strong bases such as, for example, alkali or alkaline earth amides, hydrides or hydroxides
  • Formula III generally defines the compounds to be used as starting materials for process variant (a).
  • Formula IV generally defines the diols to be used as starting materials for process variant (b).
  • the formulas Va, Vb and Vc generally define the dihydrofuran derivatives to be used as starting materials for process variant (c).
  • Formula VI generally defines the furan derivatives to be used as starting materials for process variant (d).
  • the alcoholates of the formulas VIII, VIIIb, VIIIc and VIII are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyldihydrofuran derivatives or 2-hydroxymethyl furan derivatives with suitable strong bases, such as, for example, alkali metal or alkaline earth metal amides, hydrides or hydroxides, in an inert solvent.
  • suitable strong bases such as, for example, alkali metal or alkaline earth metal amides, hydrides or hydroxides
  • the 2-hydroxymethyl derivatives mentioned are likewise known or can be prepared by known methods (cf., inter alia, H. Kröper in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, pp. 519ff [1965] and those therein literature cited).
  • Inert organic solvents are preferably suitable as diluents for the reaction according to process variant (a) according to the invention.
  • These preferably include ethers such as diethyl ether, tetrahydrofuran or dioxane, aromatic hydrocarbons such as benzene or toluene, and in individual cases also chlorinated hydrocarbons such as chloroform, methylene chloride or carbon tetrachloride.
  • reaction temperatures can be varied within a substantial range. Generally one works between 0 and 120 ° C, preferably at 20 to 100 ° C.
  • the process variant (a) according to the invention is preferably carried out in molar amounts. However, it is also possible to use the alcoholates of the formula II or the compounds of the formula III in excess of up to 1 mol.
  • water is added to the reaction mixture, the organic phase is separated off and worked up and purified in the customary manner. In individual cases, the end product can also be distilled off from the reaction product directly after the solvent.
  • the procedure is expediently started from a 2-hydroxymethyl-tetrahydrofuran derivative, the latter converted into the alkali metal alcoholate of the formula 11 in a suitable inert solvent using alkali metal hydride or amide, and the latter immediately without isolation reacted with a compound of the formula III and thus obtained the compounds of the formula according to the invention in one operation.
  • the compound of formula III can also be added to the reaction mixture before the alcoholate is prepared.
  • the preparation of the alcoholate of the formula II and the reaction according to the invention by process (a) are advantageously carried out in one Two-phase system, such as aqueous sodium or potassium hydroxide solution / toluene or methylene chloride, carried out with the addition of a phase transfer catalyst, such as ammonium or phosphonium compounds.
  • a phase transfer catalyst such as ammonium or phosphonium compounds.
  • reaction according to process variant (b) according to the invention is preferably carried out without a solvent.
  • the reaction according to the invention in process variant (b) is carried out in the presence of an acid catalyst.
  • an acid catalyst can be used. These preferably include organic acids, such as p-toluenesulfonic acid, inorganic acids, such as hydrochloric acid and sulfuric acid, and metal halides, such as aluminum chloride.
  • reaction temperatures in process variant (b) can be varied within a substantial range. Generally one works between 80 and 250 ° C, preferably between about 100 and 220 ° C.
  • reaction mixture is distilled in vacuo and the water is then separated off in the customary manner.
  • inert organic solvents are preferably suitable when using a diluent.
  • a diluent preferably include alcohols, such as methanol and ethanol, and ethers, such as diethyl ether and tetrahydrofuran.
  • the reactions according to the invention in process variants (c) and (d) are carried out in the presence of a catalyst.
  • a catalyst You can use all commonly used hydrogenation catalysts. These preferably include noble metal, noble metal oxide (or noble metal hydroxide) catalysts or so-called 'Raney catalysts', such as in particular platinum, platinum oxide, nickel, rhodium, rhodium oxide, ruthenium, palladium and osmium.
  • reaction temperatures can be varied over a wide range in process variants (c) and (d). Generally one works between 20 and 200 ° C, preferably at 80 to 150 ° C.
  • the reactions according to process variants (c) and (d) can be carried out under normal pressure, but also under elevated pressure, preferably at 1 to 200 atm.
  • the compounds of the formula according to the invention can optionally be present in different geometric isomers which can be obtained in different proportions. They are also available as optical isomers. In this case, it can occur that certain isomers have a greater activity than others, so that it may be expedient to prepare or isolate the more active components. All the isomers are claimed according to the invention.
  • the active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are all plants that 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: dicotyledon weeds of the genera: mustard (Sinapsis), cress (Lepidium), bedstraw (Galium), starwort (Stellaria), chamomile (Matricaria), dog chamomile (Anthemis), button herb (Galinsoga ), Goose foot (Chenopodium), nettle (Urtica), ragwort (Senecio), foxtail (Amaranthus), purslane (Portulaca), Norway burdock (Xanthium), winch (Convolvulus), morning glory (Ipomoea), knotweed (Polygonum), sesbanie (Sesbania ), Ambrosia (Ambrosia), Thistle (Cirsium), Thistle (Carduus), Goose Thistle (Sonchus), Nightshade (Solanum), Marsh Cress (Rorippa), Rotala, Ciderweed (Li
  • Monocot crops of the genera Rice (Orzya), Maize (Zea), Wheat (Triticum), Barley (Hordeum), Oats (Avena), Rye (Secale), Black Millet (Sorghum), Millet (Panicum), Sugar Cane (Saccharum), Pineapple (pineapple), asparagus (asparagus), leek (allium).
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops can e.g. Forestry, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.
  • the active compounds according to the invention have, in particular, strong herbicidal effects against grasses, without damaging various crop plants. They can therefore preferably be used for selective weed control.
  • the following crops are particularly suitable: beets, soybeans, beans, cotton, rapeseed, peanuts, vegetables, corn and rice.
  • the active compounds according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, 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;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural
  • the active compounds according to the invention as such or in their formulations for strengthening and supplementing their spectrum of action, can be combined with other herbicidal active compounds, depending on the intended use, finished formulations or tank mixes being possible.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90 percent by weight.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, dusting, scattering and pouring.
  • the active compounds according to the invention can be applied both after and in particular before the plants emerge. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect you want. In general, the application rates are between 0.1 and 10 kg of active ingredient per ha, preferably between 0.2 and 6 kg / ha.
  • the active compounds according to the invention not only have herbicidal properties, but also a fungicidal and insecticidal activity.
  • 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.
  • the mixture is then heated under reflux for 30 minutes, cooled to 50 ° C. and 32 g (0.2 mol) of 2-chlorobenzyl chloride are then added dropwise to the sodium salt thus obtained.
  • the mixture is then heated under reflux for a further 3 hours, 20 ml of methanol are added to destroy excess sodium hydride and the mixture is concentrated by distilling off the solvent in vacuo.

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

Description

Die Erfindung betrifft Tetrahydrofuran-Derivate, mehrere Verfahren zu ihrer Herstellung sowie ihre Verwendung als Herbizide, insbesondere als selektive Herbizide.The invention relates to tetrahydrofuran derivatives, several processes for their preparation and their use as herbicides, in particular as selective herbicides.

Es ist bereits bekannt geworden, daß Chloracetanilide, wie beispielsweise 2-Aethyl-6-methyl-N-(1'-methyl-2'-methoxyäthyl)chloracetanilid, als Herbizide, insbesondere zur Bekämpfung von grasartigen Unkräutern, verwendet werden können (vgl. DE-A-2 328 340). Diese Verbindungen sind in ihrer Selektivität jedoch nicht immer befriedigend.It has already become known that chloroacetanilides, such as, for example, 2-ethyl-6-methyl-N- (1'-methyl-2'-methoxyethyl) chloroacetanilide, can be used as herbicides, in particular for controlling grass-like weeds (cf. DE-A-2 328 340). However, the selectivity of these compounds is not always satisfactory.

Es wurden Tetrahydrofuran-Derivate der Formel I

Figure imgb0001
in welcher

  • R1 bis R6 gleich oder verschieden sind und für Wasserstoff, geradkettiges oder verzweigtes C1_8‾- Alkyl, C1-2-Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wobei als Halogene insbesondere Fluor, Chlor und Brom stehen), Alkoxyalkyl mit 1 oder 2 C-Atomen in jedem Alkylteil, sowie für jeweils gegebenenfalls durch Halogen, C1-2-Alkyl, C1-2-Alkoxy oder C1-2-Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wie insbesondere Fluor und Chlor) substituiertes Phenyl oder Benzyloxyalkyl mit 1 oder 2 C-Atomen im Alkylteil stehen,
  • R5 und R6 auch gemeinsam für einen gesättigten carbocyclischen Ring mit insgesamt 3 bis 6 C-Atomen stehen,
  • R7 für Wasserstoff, geradkettiges oder verzweigtes C1-6-Alkyl, C3-6-Cycloalkyl, C2-4-Alkenyl, C2-4- Alkinyl, Alkoxyalkyl mit 1 bis 2 C-Atomen in jedem Alkylteil, sowie für jeweils durch Halogen, C1-2-Alkyl, C1-2-Alkoxy, oder C1-2-Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wie insbesondere Fluor und Chlor) substituiertes Phenyl oder Benzyloxyalkyl mit 1 oder 2 C-Atomen im Alkylteil steht,
  • R^ und R9 gleich oder verschieden sind und für Wasserstoff, geradkettiges oder verzweigtes C1-6- Alkyl, C2-4-Alkenyl, C2-4-Alkinyl, C3-6-Cycloalkyl, C1-4-Alkoxy, sowie für jeweils gegebenenfalls durch Halogen, C1-2-Alkyl, C1-2-Alkoxy oder C1-2-Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wie insbesondere Fluor und Chlor) substituiertes Phenyl, Benzyl oder Benzyloxy stehen,
  • R10 für Wasserstoff, geradkettiges oder verzweigtes C1-6-Alkyl, C2-4-Alkenyl, C2-4-Alkinyl, C1-2 Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wobei als Halogene insbesondere Fluor, Chlor oder Brom stehen), sowie für gegebenenfalls durch Halogen, C1-2-Alkyl, C1-2-Alkoxy oder C1-2-Halogenalkyl mit bis zu drei gleichen oder verschiedenen Halogenatomen (wie insbesondere Fluor und Chlor) substituiertes Phenyl steht und
  • Y für gegebenenfalls substituiertes Aryl mit 6 bis 10 C-Atomen (insbesondere für Phenyl und Naphthyl) steht, welches einen oder mehrere gleiche oder verschiedene der folgenden Substituenten tragen kann: die Halogene Fluor, Chlor oder Brom; Alkyl und Alkoxy mit jeweils 1 bis 4 C-Atomen; Halogenalkyl, Halogenalkoxy und Halogenalkylthio mit jeweils bis zu 4 C-Atomen und bis zu 5 Halogenatomen (insbesondere mit bis zu 2 C-Atomen und bis zu 3 gleichen oder verschiedenen Halogenatomen, wobei als Halogene insbesondere Fluor, Chlor und Brom stehen); gegebenenfalls durch Halogen, (insbesondere Fluor, Chlor oder Brom), Alkyl und Alkoxy mit jeweils 1 bis 2 C-Atomen sowie Halogenalkyl mit bis zu 2 C-Atomen und bis zu 3 gleichen oder verschiedenen Halogenatomen (wie insbesondere Fluor und Chlor), substituiertes Phenyl, Phenoxy oder Phenoxycarbonyl; Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkylteil; die Methylendioxy-Gruppe sowie den Tri-, Tetra- oder Pentamethylen-Rest; mit der Maßgabe, daß, falls Y für Phenyl steht, dieses substituiert sein muß, wenn R1 bis R10 Wasserstoff bedeuten,

aufgefunden.There were tetrahydrofuran derivatives of the formula I.
Figure imgb0001
 in which
  • R 1 to R 6 are the same or different and represent hydrogen, straight-chain or branched C 1 _ 8 ‾-alkyl, C 1-2 -haloalkyl with up to three identical or different halogen atoms (where halogen, in particular fluorine, chlorine and bromine) , Alkoxyalkyl with 1 or 2 carbon atoms in each alkyl part, and for each optionally by halogen, C 1-2 alkyl, C 1-2 alkoxy or C 1-2 haloalkyl with up to three identical or different halogen atoms (such as especially fluorine and chlorine) substituted phenyl or benzyloxyalkyl with 1 or 2 carbon atoms in the alkyl part,
  • R 5 and R 6 also together represent a saturated carbocyclic ring with a total of 3 to 6 carbon atoms,
  • R 7 is hydrogen, straight-chain or branched C 1-6 alkyl, C 3-6 cycloalkyl, C 2-4 alkenyl, C 2-4 alkynyl, alkoxyalkyl with 1 to 2 C atoms in each alkyl part, and for each phenyl or benzyloxyalkyl with 1 or 2 C- substituted by halogen, C 1-2 alkyl, C 1-2 alkoxy, or C 1-2 haloalkyl with up to three identical or different halogen atoms (such as especially fluorine and chlorine) Atoms in the alkyl part,
  • R ^ and R 9 are the same or different and are hydrogen, straight-chain or branched C 1-6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 1-4 alkoxy , as well as phenyl, benzyl or benzyloxy which are optionally substituted by halogen, C 1-2 alkyl, C 1-2 alkoxy or C 1-2 haloalkyl with up to three identical or different halogen atoms (such as in particular fluorine and chlorine) ,
  • R 10 represents hydrogen, straight-chain or branched C 1-6 -alkyl, C 2-4 -alkenyl, C 2-4 -alkynyl, C 1-2 haloalkyl with up to three identical or different halogen atoms (as halogen, in particular fluorine, chlorine or bromine), and represents phenyl optionally substituted by halogen, C 1-2 alkyl, C 1-2 alkoxy or C 1-2 haloalkyl with up to three identical or different halogen atoms (such as in particular fluorine and chlorine) and
  • Y represents optionally substituted aryl having 6 to 10 carbon atoms (in particular phenyl and naphthyl), which can carry one or more identical or different of the following substituents: the halogens fluorine, chlorine or bromine; Alkyl and alkoxy, each with 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio, each with up to 4 C atoms and up to 5 halogen atoms (in particular with up to 2 C atoms and up to 3 identical or different halogen atoms, the halogen being in particular fluorine, chlorine and bromine); optionally substituted by halogen, (in particular fluorine, chlorine or bromine), alkyl and alkoxy each having 1 to 2 carbon atoms and halogenoalkyl having up to 2 carbon atoms and up to 3 identical or different halogen atoms (such as in particular fluorine and chlorine) Phenyl, phenoxy or phenoxycarbonyl; Alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part; the methylenedioxy group and the tri, tetra or pentamethylene radical; with the proviso that if Y is phenyl, it must be substituted when R 1 to R 10 are hydrogen,

found.

Diese Tetrahydrofuran-Derivate weisen starke herbizide, insbesondere selektiv-herbizide Eigenschaften auf.These tetrahydrofuran derivatives have strong herbicidal, in particular selective herbicidal properties.

Weiterhin wurde gefunden, daß man die Tetrahydrofuran-Derivate der Formel 1 erhält, wenn man

  • (a) Alkoholate von 2-Hydroxymethyl-tetrahydrofuran-Derivaten der Formel II
    Figure imgb0002
    in welcher
    • R1 bis R9 die oben angegebene Bedeutung haben und
    • M für ein Alkali- oder Erdalkalimetall (insbesondere für Natrium und Kalium sowie für 1 Äquivalent Magnesium und Calcium) steht,
    • mit einer Verbindung der Formel III
      Figure imgb0003
      in welcher
    • R10 und Y die oben angegebene Bedeutung haben und
    • Z für Halogen (insbesondere Chlor oder Brom), den Mesylat- oder Tosylat-Rest steht,

    in an sich bekannter Weise, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man
  • (b) Diole der Formel IV
    Figure imgb0004
    in welcher
    • R1 bis R10 und
    • Y die oben angegebene Bedeutung haben,

    in an sich bekannter Weise in Gegenwart eines sauren Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels erhitzt.
Furthermore, it was found that the tetrahydrofuran derivatives of the formula 1 are obtained when
  • (a) Alcoholates of 2-hydroxymethyl-tetrahydrofuran derivatives of the formula II
    Figure imgb0002
     in which
    • R 1 to R 9 have the meaning given above and
    • M stands for an alkali or alkaline earth metal (in particular for sodium and potassium and for 1 equivalent of magnesium and calcium),
    • with a compound of formula III
      Figure imgb0003
       in which
    • R 10 and Y have the meaning given above and
    • Z represents halogen (in particular chlorine or bromine), the mesylate or tosylate radical,

    in a manner known per se, if appropriate in the presence of a diluent, or if one
  • (b) Diols of formula IV
    Figure imgb0004
     in which
    • R 1 to R 10 and
    • Y have the meaning given above,

    heated in a conventional manner in the presence of an acid catalyst and optionally in the presence of a diluent.

Verbindungen der Formel I, in denen entweder R1 und R7 oder R1 und R4 oder R4 und R5 für Wasserstoff stehen, können auch erhalten werden, wenn man

  • (c) Dihydrofuran-Derivate der Formeln Va, Vb und Vc
    Figure imgb0005
    Figure imgb0006
    und/oder
    Figure imgb0007
    in welchen
    • R1 bis R10 und
    • Y die oben angegebene Bedeutung haben,

    in an sich bekannter Weise in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert.
Compounds of the formula I in which either R 1 and R 7 or R 1 and R 4 or R 4 and R 5 are hydrogen can also be obtained if
  • (c) Dihydrofuran derivatives of the formulas Va, Vb and Vc
    Figure imgb0005
    Figure imgb0006
     and or
    Figure imgb0007
     in which
    • R 1 to R 10 and
    • Y have the meaning given above,

    hydrogenated in a conventional manner in the presence of a catalyst and optionally in the presence of a diluent with hydrogen.

Verbindungen der Formel l, in denen R1, R4, R5 und R7 für Wasserstoff stehen, können auch erhalten werden, wenn man

  • (d) Furan-Derivate der Formel VI
    Figure imgb0008
    in welcher
    • R2, R3, R6, R8, R9, R10 und Y die oben angegebene Bedeutung haben,

    in an sich bekannter Weise in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert.
Compounds of the formula I in which R 1 , R 4 , R 5 and R 7 are hydrogen can also be obtained if
  • (d) Furan derivatives of the formula VI
    Figure imgb0008
     in which
    • R 2 , R 3 , R 6 , R 8 , R 9 , R 10 and Y have the meaning given above,

    hydrogenated in a conventional manner in the presence of a catalyst and optionally in the presence of a diluent with hydrogen.

Ueberraschenderweise sind die erfindungsgemäßen Tetrahydrofuran-Derivate den bekannten Gräserbekämpfungsmitteln, wie beispielsweise 2 - Aethyl - 6 - methyl - N - (1' - methyl - 2' - methoxyäthyl) - chloracetanilid, in der herbiziden Wirkung überlegen und zeigen außerdem eine aeutlich bessere Selektivität gegenüber wichtigen Kulfurpflanzen. Die erfindungsgemäßen Wirkstoffe stellen somit eine wesentliche Bereicherung der herbiziden Mittel, insbesondere der Gräserherbizide, dar.Surprisingly, the tetrahydrofuran derivatives according to the invention are superior to the known herbicides, such as, for example, 2-ethyl-6-methyl-N - (1'-methyl-2'-methoxyethyl) -chloroacetanilide, in their herbicidal action and also show a markedly better selectivity important kulfur plants. The active compounds according to the invention thus represent a significant enrichment of herbicides, especially grass herbicides.

Verwendet man das Natriumalkoholat des Tetrahydrofurfurylalkohols und 2-Fluorbenzylbromid als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden (Verfahrensvariante a):

Figure imgb0009
If the sodium alcoholate of tetrahydrofurfuryl alcohol and 2-fluorobenzyl bromide are used as starting materials, the course of the reaction can be represented by the following formula (process variant a):
Figure imgb0009

Verwendet man 1-(2-Fluorbenzyloxy)-pentan-2,5-diol als Ausgangsstoff und p-Toluolsulfonsäure als Katalysator, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden (Verfahrensvariante b):

Figure imgb0010
If 1- (2-fluorobenzyloxy) pentane-2,5-diol is used as the starting material and p-toluenesulfonic acid is used as the catalyst, the course of the reaction can be represented by the following formula (process variant b):
Figure imgb0010

Verwendet man 2,3-Dihydro-2-(2-Fluorbenzyloxymethyl)-furan und Wasserstoff als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden (Verfahrens - variante c):

Figure imgb0011
If 2,3-dihydro-2- (2-fluorobenzyloxymethyl) furan and hydrogen are used as starting materials, the course of the reaction can be represented by the following formula (process variant c):
Figure imgb0011

Verwendet man 2-[1-(2-Chlorbenzyloxy)-prop-1-yl]-furan und Wasserstoff als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden (Verfahrensvariante d):

Figure imgb0012
If 2- [1- (2-chlorobenzyloxy) prop-1-yl] furan and hydrogen are used as starting materials, the course of the reaction can be represented by the following formula (process variant d):
Figure imgb0012

Die Alkoholate der Formel II sind bekannt oder lassen sich nach bekannten Methoden herstelien. Man erhält sie z.B., indem man die entsprechenden 2-Hydroxymethyl-tetrahydrofuran-Derivate mit geeigneten starken Basen, wie beispielsweise Alkali- bzw. Erdalkaliamiden, -hydriden oder -hydroxiden, in einem inerten Lösungsmittel umsetzt. Die genannten 2-Hydroxymethyl-tetrahydrofuran-Derivate sind ebenfalls bekannt oder lassen sich nach bekannten Methoden herstellen (vgl. u.a. H.Kröper, in Houben-Weyl, 'Methoden der organischen Chemie', Band 6/3, S.519ff [1965] sowie die dort zitierte Literatur).The alcoholates of the formula II are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyltetrahydrofuran derivatives with suitable strong bases, such as, for example, alkali or alkaline earth amides, hydrides or hydroxides, in an inert solvent. The 2-hydroxymethyl-tetrahydrofuran derivatives mentioned are likewise known or can be prepared by known methods (cf., inter alia, H. Kröper, in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, p.519ff [1965] as well as the literature cited there).

Als Beispiele für die 2-Hydroxymethyl-tetrahydrofuran-Derivate, die den erfindungsgemäß als Ausgangsstoffe zu verwendenden Alkoholaten der Formel II zugrunde liegen, seien genannt:

  • 2-Hydroxymethyl-tetrahydrofuran
  • 2-( -Hydroxyprop-1 -yi)-tetrahydrofuran
  • 2-( 1-Hydroxyäthyl)-tetrahydrofuran
  • 2-(3-Hydroxypent-3-yl)-tetrahydrofuran
  • 2-(Hydroxy-phenyl-methyl)-tetrahydrofuran
  • 2-(2-Hydroxyprop-2-yl)-tetrahydrofuran
Examples of the 2-hydroxymethyl-tetrahydrofuran derivatives on which the alcoholates of the formula II to be used according to the invention are based are:
  • 2-hydroxymethyl tetrahydrofuran
  • 2- (-hydroxyprop-1-yi) tetrahydrofuran
  • 2- (1-hydroxyethyl) tetrahydrofuran
  • 2- (3-hydroxypent-3-yl) tetrahydrofuran
  • 2- (hydroxyphenylmethyl) tetrahydrofuran
  • 2- (2-hydroxyprop-2-yl) tetrahydrofuran

Die weiterhin für die Verfahrensvariante (a) als Ausgangstoffe zu verwendenden Verbindungen sind durch die Formel III allgemein definiert.Formula III generally defines the compounds to be used as starting materials for process variant (a).

Die Ausgangsstoffe der Formel III sind allgemein bekannte Verbindungen der organischen Chemie. Als Beispiele seien genannt:

  • Benzylchlorid, Benzylbromid, Benzylmesylat, Benzyltosylat, 2-Fluorbenzylbromid, 3-Fluorbenzylbromid, 4-Fluorbenzylbromid, 2-Chlorbenzylchlorid, 3-Chlorbenzylchlorid, 4-Chlorbenzylchlorid, 2-Brombenzylchlorid, 3-Brombenzylchlorid, 4-Brombenzylchlorid, 2-Methylbenzylchlorid, 3-Methylbenzylchlorid, 4-Methylbenzylchlorid, 2-Methoxybenzylchlorid, 3-Methoxybenzylchlorid, 4-Methoxybenzylchlorid, 2-Trifluormethylbenzylchlorid, 3-Trifluormethylbenzylchlorid, 4-Trifluormethylbenzylchlorid, 4-Phenylbenzylchlorid, 2,6-Difluorbenzylchlorid, 2,6-Dichlorbenzylchlorid, 2,4-Dichlorbenzylchlorid, 3,4-Dichlorbenzylchlorid, 2,5-Dichlorbenzylchlorid, 2,6-Dimethylbenzylchlorid, 2,4-Dimethylbenzylbromid, 3,4-Dimethylbenzylchlorid, 2,3-Dimethylbenzylchlorid, 3,4-Dioxymethylenbenzylchlorid, 2,6-Chlorfluorbenzylchlorid, 2-Fluor-5-chlorbenzylbromid, 2-Fluor-4-chlorbenzylbromid, 3-Chlor-4-fluorbenzylbromid, 3,4-Tetramethylenbenzylchlorid, 2-Methyl-6-chlorbenzylchlorid, 2-Methyl-6-fluorbenzyl- chlorid, 2-Fluor-3-methylbenzylchlorid, 2-Fluor-4-methylbenzylchlorid, 2-Fluor-5-methylbenzylchlorid, 2-Methyl-3-chlorbenzylchlorid, 2-Methyl-4-chlorbenzylchlorid, 2-Methyl-5-chlorbenzylchlorid, 2,4,5-Trichlorbenzylbromid, 2,4,6-Trichlorbenzylbromid, Diphenylmethylbromid, 1-Brom-1-phenyläthan, 1-Brom-1-(2-fluorphenyl)-äthan, 1-Brom-1-(2-methylphenyl)-äthan.
The starting materials of formula III are generally known compounds of organic chemistry. Examples include:
  • Benzyl chloride, benzyl bromide, benzyl mesylate, benzyl tosylate, 2-fluorobenzyl bromide, 3-fluorobenzyl bromide, 4-fluorobenzyl bromide, 2-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-chlorobenzyl chloride, 2-bromobenzyl chloride, 3-bromobenzyl chloride, 4-bromobenzyl chloride, 4-bromobenzyl chloride, 4-bromobenzyl chloride, 4-bromobenzyl chloride Methylbenzyl chloride, 4-methylbenzyl chloride, 2-methoxybenzyl chloride, 3-methoxybenzyl chloride, 4-methoxybenzyl chloride, 2-trifluoromethylbenzyl chloride, 3-trifluoromethylbenzyl chloride, 4-trifluoromethylbenzyl chloride, 4-phenylbenzyl chloride, 2,6-difluorobenzyl chloride, 2,6-dichlorobenzyl chloride, Dichlorobenzyl chloride, 3,4-dichlorobenzyl chloride, 2,5-dichlorobenzyl chloride, 2,6-dimethylbenzyl chloride, 2,4-dimethylbenzyl bromide, 3,4-dimethylbenzyl chloride, 2,3-dimethylbenzyl chloride, 3,4-dioxymethylenebenzyl chloride, 2,6-chlorofluorobenzyl chloride, 2-fluoro-5-chlorobenzyl bromide, 2-fluoro-4-chlorobenzyl bromide, 3-chloro-4-fluorobenzyl bromide, 3,4-tetramethylene benzyl chloride, 2-methyl-6-chlorobenzyl chloride, 2-methyl-6-fluorobenzyl chloride, 2-fluoro-3-methylbenzyl chloride, 2-fluoro-4-methylbenzyl chloride, 2-fluoro-5-methylbenzyl chloride, 2-methyl-3-chlorobenzyl chloride, 2-methyl-4-chlorobenzyl chloride, 2-methyl-5-chlorobenzyl chloride, 2,4,5-trichlorobenzyl bromide, 2,4,6-trichlorobenzyl bromide, diphenylmethyl bromide, 1-bromo-1-phenylethane, 1-bromo-1- (2-fluorophenyl) -ethane, 1-bromo-1- (2-methylphenyl) -ethane.

Die für die Verfahrensvariante (b) als Ausgangsstoffe zu verwendenden Diole sind durch die Formel IV allgemein definiert.Formula IV generally defines the diols to be used as starting materials for process variant (b).

Die Diole der Formel IV sind bekannt bzw. lassen sie sich nach bekannten Methoden herstellen. Als Beispiele seien genannt:

  • 1-Benzyloxy-pentan-2,5-diol
  • 1-(2-Fluorbenzyloxy)-pentan-2,5-diol
  • 1-(2-Chlorbenzyloxy)-pentan-2,5-diol
  • 1-(2-Methylbenzyloxy)-pentan-2,5-diol
  • 1-(2-Brombenzyloxy)-pentan-2,5-diol
  • 1-(4-Fluorbenzyloxy)-pentan-2,5-diol
  • 1-(2,6-Dichlorbenzyloxy)-pentan-2,5-diol
  • 1-Benzyloxy-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Fluorbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Chlorbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Methylbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Brombenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1-(4-Fluorbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1-(2,6-Dichlorbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • 1 -Benzyloxy-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(2-Fluorbenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(2-Chlorbenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(2-Methylbenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(2-Brombenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(4-Fluorbenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-(2,6-Dichlorbenzyloxy)-2,5,5-trimethyl-pentan-2,5-diol
  • 1-Benzyloxy-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Fluorbenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Chlorbenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Methylbenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(2-Brombenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(4-Fluorbenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
  • 1-(2,6-Dichlorbenzyloxy)-2-äthyl-5,5-dimethyl-pentan-2,5-diol
The diols of the formula IV are known or they can be prepared by known methods. Examples include:
  • 1-benzyloxy-pentane-2,5-diol
  • 1- (2-fluorobenzyloxy) pentane-2,5-diol
  • 1- (2-chlorobenzyloxy) pentane-2,5-diol
  • 1- (2-methylbenzyloxy) pentane-2,5-diol
  • 1- (2-bromobenzyloxy) pentane-2,5-diol
  • 1- (4-fluorobenzyloxy) pentane-2,5-diol
  • 1- (2,6-dichlorobenzyloxy) pentane-2,5-diol
  • 1-benzyloxy-5,5-dimethyl-pentane-2,5-diol
  • 1- (2-fluorobenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (2-chlorobenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (2-methylbenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (2-bromobenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (4-fluorobenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (2,6-dichlorobenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1-benzyloxy-2,5,5-trimethyl-pentane-2,5-diol
  • 1- (2-fluorobenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1- (2-chlorobenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1- (2-methylbenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1- (2-bromobenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1- (4-fluorobenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1- (2,6-dichlorobenzyloxy) -2,5,5-trimethylpentan-2,5-diol
  • 1-benzyloxy-2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (2-fluorobenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (2-chlorobenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (2-methylbenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (2-bromobenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (4-fluorobenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol
  • 1- (2,6-dichlorobenzyloxy) -2-ethyl-5,5-dimethyl-pentane-2,5-diol

Die für die Verfahrensvariante (c) als Ausgangsstoffe zu verwendenden Dihydrofuran-Derivate sind durch die Formeln Va, Vb und Vc allgemein definiert.The formulas Va, Vb and Vc generally define the dihydrofuran derivatives to be used as starting materials for process variant (c).

Die Dihydrofuran-Derivate der Formeln Va, Vb und Vc sind noch nicht bekannt, Man erhält sie jedoch auf einfache Weise, wenn man entsprechend der Verfahrensvariante (a) Alkoholate von 2-Hydroxymethyl-dihydrofuran-Derivaten der Formeln Vlla, Vllb und Vllc

Figure imgb0013
Figure imgb0014
Figure imgb0015
in welchen

  • R' bis R9 und
  • M die oben angegebene Bedeutung haben,
  • mit einer Verbindung der Formel III gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.
The dihydrofuran derivatives of the formulas Va, Vb and Vc are not yet known, but they can be obtained in a simple manner if, according to process variant (a), alcoholates of 2-hydroxymethyl-dihydrofuran derivatives of the formulas VIIa, Vllb and Vllc
Figure imgb0013
Figure imgb0014
Figure imgb0015
 in which
  • R 'to R 9 and
  • M have the meaning given above,
  • with a compound of formula III if appropriate in the presence of a diluent.

Die für die Verfahrensvariante (d) als Ausgangsstoffe zu verwendenden Furan-Derivate sind durch die Formel VI allgemein definiert.Formula VI generally defines the furan derivatives to be used as starting materials for process variant (d).

Die Furan-Derivate der Formel VI sind noch nicht bekannt. Man erhält sie jedoch auf einfache Weise, wenn man entsprechend der Verfahrensvariante (a) Alkoholate von 2-Hydroxymethyl-furanDerivaten der Formel VIII

Figure imgb0016
in welcher

  • R 2, R3, R°, R", R9 und M die oben angegebene Bedeutung haben,

mit einer Verbindung der-Formel III gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.The furan derivatives of the formula VI are not yet known. However, they are obtained in a simple manner if, according to process variant (a), alcoholates of 2-hydroxymethyl-furan derivatives of the formula VIII
Figure imgb0016
 in which
  • R 2 , R 3 , R °, R ", R 9 and M have the meaning given above,

with a compound of the formula III, if appropriate in the presence of a diluent.

Als Ausgangsstoffe der Formel VI seien beispielsweise genannt:

  • 2-(2-Fluorbenzyloxymethyl)-furan
  • 2-[1-(2-Fluorbenzyloxy)-äth-1-yl]-furan
  • 2-[1-(2-Chlorbenzyloxy)-prop-1-yl]-furan
  • 2-[1-(2-Fluorbenzyloxy)-prop-1-yl]-furan
  • 2-[1-(2-Fluorbenzyloxy)-äth-1-yl]-furan
  • 2-[1-(2-Methylbenzyloxy)-äth-1-yl]-furan
  • 2-[1-(Benzyloxy)-äth-1-yl]-furan
  • 2-[3-(2-Fluorbenzyloxy-pent-3-yl]-furan
  • 2-[3-(2-Methylbenzyfoxy)-pent-3-yl]-furan
  • 2-[3-(2-Chlorbenzyloxy)-pent-3-yl]-furan
  • 2-[ 1-(2-Chlorbenzyloxy)-äth-1-yl]-furan
  • 2-[α-(2-Fluorbenzyloxy)-benzyl]-furan
  • 2-[α-(2-chlorbenzyloxy)-benzyl]-furan
  • 2-[2-(2-Fluorbenzyloxy)-prop-2-yl]-furan
  • 2-(a-Phenylbenzyloxy-methyl)-furan
The following may be mentioned as starting materials of the formula VI:
  • 2- (2-fluorobenzyloxymethyl) furan
  • 2- [1- (2-fluorobenzyloxy) eth-1-yl] furan
  • 2- [1- (2-chlorobenzyloxy) prop-1-yl] furan
  • 2- [1- (2-fluorobenzyloxy) prop-1-yl] furan
  • 2- [1- (2-fluorobenzyloxy) eth-1-yl] furan
  • 2- [1- (2-methylbenzyloxy) eth-1-yl] furan
  • 2- [1- (benzyloxy) eth-1-yl] furan
  • 2- [3- (2-fluorobenzyloxy-pent-3-yl] furan
  • 2- [3- (2-Methylbenzyfoxy) pent-3-yl] furan
  • 2- [3- (2-chlorobenzyloxy) pent-3-yl] furan
  • 2- [1- (2-chlorobenzyloxy) eth-1-yl] furan
  • 2- [α- (2-fluorobenzyloxy) benzyl] furan
  • 2- [α- (2-chlorobenzyloxy) benzyl] furan
  • 2- [2- (2-fluorobenzyloxy) prop-2-yl] furan
  • 2- (a-phenylbenzyloxy-methyl) furan

Die Alkoholate der Formeln Vlla, Vllb, Vllc und VIII sind bekannt oder lassen sich nach bekannten Methoden herstellen. Man erhält sie z.B., indem man die entsprechenden 2-Hydroxymethyldihydrofuran-Derivate bzw. 2-Hydroxymethyl-furan-Derivate mit geeigneten starken Basen, wie beispielsweise Alkali- oder Erdalkaliamiden, -hydriden oder -hydroxiden, in einem inerten Lösungsmittel umsetzt. Die genannten 2-Hydroxymethyl-Derivate sind ebenfalls bekannt oder lassen sich nach bekannten Methoden herstellen (vgl. u.a. H.Kröper in Houben-Weyl, 'Methoden der organischen Chemie', Band 6/3, S.519ff [1965] sowie die dort zitierte Literatur).The alcoholates of the formulas VIII, VIIIb, VIIIc and VIII are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyldihydrofuran derivatives or 2-hydroxymethyl furan derivatives with suitable strong bases, such as, for example, alkali metal or alkaline earth metal amides, hydrides or hydroxides, in an inert solvent. The 2-hydroxymethyl derivatives mentioned are likewise known or can be prepared by known methods (cf., inter alia, H. Kröper in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, pp. 519ff [1965] and those therein literature cited).

Für die erfindungsgemäße Umsetzung gemäß Verfahrensvariante (a) kommen als Verdünnungsmittel vorzugsweise inerte organische Lösungsmittel infrage. Hierzu gehören vorzugsweise Aether, wie Diäthyläther, Tetrahydrofuran oder Dioxan, aromatische Kohlenwasserstoffe, wie Benzol oder Toluol, in einzelnen Fällen auch chlorierte Kohlenwasserstoffe, wie Chloroform, Methylenchlorid oder Tetrachlorkohlenstoff.Inert organic solvents are preferably suitable as diluents for the reaction according to process variant (a) according to the invention. These preferably include ethers such as diethyl ether, tetrahydrofuran or dioxane, aromatic hydrocarbons such as benzene or toluene, and in individual cases also chlorinated hydrocarbons such as chloroform, methylene chloride or carbon tetrachloride.

Die Reaktionstemperaturen können bei der Verfahrensvariante (a) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen 0 und 120°C, vorzugsweise bei 20 bis 100°C. Bei der Durchführung der erfindungsgemäßen Verfahrensvariante (a) arbeitet man vorzugsweise in molaren Mengen. Es ist aber auch möglich, die Alkoholate der Formel II oder die Verbindungen der Formel III im Ueberschuß bis zu 1 Mol einzusetzen. Zur Isolierung der Endprodukte wird das Reaktionsgemisch mit Wasser versetzt, die organische Phase abgetrennt und in üblicher Weise aufgearbeitet und gereinigt. In einzelnen Fällen kann das Endprodukt auch direkt nach dem Lösungsmittel aus dem Rekationsprodukt abdestilliert werden.In process variant (a), the reaction temperatures can be varied within a substantial range. Generally one works between 0 and 120 ° C, preferably at 20 to 100 ° C. The process variant (a) according to the invention is preferably carried out in molar amounts. However, it is also possible to use the alcoholates of the formula II or the compounds of the formula III in excess of up to 1 mol. To isolate the end products, water is added to the reaction mixture, the organic phase is separated off and worked up and purified in the customary manner. In individual cases, the end product can also be distilled off from the reaction product directly after the solvent.

Nach einer bevorzugten Ausführungsform wird zweckmäßigerweise so verfahren, daß man von einem 2-Hydroxymethyl-tetrahydrofuran-Derivat ausgeht, letzteres in einem geeigneten inerten Lösungsmittel mittels Alkalimetall-hydrid oder -amid in das Alkalimetall-alkoholat der Formel 11 überführt, und letzteres ohne Isolierung sofort mit einer Verbindung der Formel III umsetzt und somit die erfindungsgemäßen Verbindungen der Formel in einem Arbeitsgang erhält. Dabei kann die Verbindung der Formel III auch bereits vor der Herstellung des Alkoholats dem Reaktionsgemisch zugesetzt werden.According to a preferred embodiment, the procedure is expediently started from a 2-hydroxymethyl-tetrahydrofuran derivative, the latter converted into the alkali metal alcoholate of the formula 11 in a suitable inert solvent using alkali metal hydride or amide, and the latter immediately without isolation reacted with a compound of the formula III and thus obtained the compounds of the formula according to the invention in one operation. The compound of formula III can also be added to the reaction mixture before the alcoholate is prepared.

Nach einer weiteren bevorzugten Ausführungsform werden zweckmäßigerweise die Herstellung des Alkoholats der Formel II sowie die erfindungsgemäße Umsetzung nach Verfahren (a) in einem Zweiphasensystem, wie z.B. wässrige Natron- oder Kalilauge/Toluol oder Methylenchlorid, unter Zusatz eines Phasen-Transfer-Katalysators, wie beispielsweise Ammonium- oder Phosphoniumverbindungen durchgeführt.According to a further preferred embodiment, the preparation of the alcoholate of the formula II and the reaction according to the invention by process (a) are advantageously carried out in one Two-phase system, such as aqueous sodium or potassium hydroxide solution / toluene or methylene chloride, carried out with the addition of a phase transfer catalyst, such as ammonium or phosphonium compounds.

Die erfindungsgemäße Umsetzung gemäß Verfahrensvariante (b) wird vorzugsweise ohne Lösungsmittel durchgeführt.The reaction according to process variant (b) according to the invention is preferably carried out without a solvent.

Die erfindungsgemäße Umsetzung gemäß Verfahrensvariante (b) wird in Gegenwart eines sauren Katalysators durchgeführt. Man kann alle üblicherweise verwendbaren anorganischen und organischen sauren Katalysatoren einsetzen. Hierzu gehören vorzugsweise organische Säuren, wie p-Toluolsulfonsäure, anorganische Säuren, wie Salzsäure und Schwefelsäure, sowie Metallhalogenide, wie Aluminiumchlorid.The reaction according to the invention in process variant (b) is carried out in the presence of an acid catalyst. All commonly used inorganic and organic acid catalysts can be used. These preferably include organic acids, such as p-toluenesulfonic acid, inorganic acids, such as hydrochloric acid and sulfuric acid, and metal halides, such as aluminum chloride.

Die Reaktionstemperaturen können bei der Verfahrensvariante (b) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen 80 und 250°C, vorzugsweise zwischen etwa 100 und 220°C.The reaction temperatures in process variant (b) can be varied within a substantial range. Generally one works between 80 and 250 ° C, preferably between about 100 and 220 ° C.

Zur Isolierung der Endprodukte wird bei der Verfahrensvariante (b) das Reaktionsgemisch im Vakuum destilliert und anschließend das Wasser in üblicher Weise abgetrennt.To isolate the end products in process variant (b), the reaction mixture is distilled in vacuo and the water is then separated off in the customary manner.

Für die erfindungsgemaßen Umsetzungen gemäß Verfahrensvarianten (c) und (d) kommen bei Verwendung eines Verdünnungsmittels vorzugsweise inerte organische Lösungsmittel infrage. Hierzu gehören vorzugsweise Alkohole, wie Methanol und Aethanol sowie Aether, wie Diäthyläther und Tetrahydrofuran.For the reactions according to the invention according to process variants (c) and (d), inert organic solvents are preferably suitable when using a diluent. These preferably include alcohols, such as methanol and ethanol, and ethers, such as diethyl ether and tetrahydrofuran.

Die erfindungsgemäßen Umsetzungen gemäß Verfahrensvarianten (c) und (d) werden in Gegenwart eines Katalysators durchgeführt. Man kann alle üblicherweise verwendbaren Hydrierungskatalysatoren verwenden. Hierzu gehören vorzugsweise Edelmetall-, Edelmetalloxid- (bzw. Edelmetallhydroxid-) -Katalysatoren oder sogenannte 'Raney-Katalysatoren', wie insbesondere Platin, Platinoxid, Nickel, Rhodium, Rhodiumoxid, Ruthenium, Palladium und Osmium.The reactions according to the invention in process variants (c) and (d) are carried out in the presence of a catalyst. You can use all commonly used hydrogenation catalysts. These preferably include noble metal, noble metal oxide (or noble metal hydroxide) catalysts or so-called 'Raney catalysts', such as in particular platinum, platinum oxide, nickel, rhodium, rhodium oxide, ruthenium, palladium and osmium.

Die Reaktionstemperaturen können bei den Verfahrensvarianten (c) und (d) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen 20 und 200°C, vorzugsweise bei 80 bis 150°C.The reaction temperatures can be varied over a wide range in process variants (c) and (d). Generally one works between 20 and 200 ° C, preferably at 80 to 150 ° C.

Die Umsetzungen gemäß Verfahrensvarianten (c) und (d) können bei Normaldruck, aber auch bei erhöhtem Druck, vorzugsweise bei 1 bis 200 atü, durchgeführt werden.The reactions according to process variants (c) and (d) can be carried out under normal pressure, but also under elevated pressure, preferably at 1 to 200 atm.

Bei der Durchführung der erfindungsgemäßen Verfahrensvarianten (c) und (d) setzt man auf 1 Mol der Verbindungen der Formeln Va, Vb, Vc, bzw. VI vorzugsweise 2 Mol Wasserstoff und 0,01-0,1 Mol Katalysator ein. Zur Isolierung der Endprodukte wird vom Katalysator abfiltriert, gegebenenfalls vom Lösungsmittel im Vakuum befreit und die erhaltenen Produkte der Formel I werden durch Destillation oder Umkristallisation gereinigt.When carrying out process variants (c) and (d) according to the invention, 2 mol of hydrogen and 0.01-0.1 mol of catalyst are preferably employed per mol of the compounds of the formulas Va, Vb, Vc or VI. To isolate the end products, the catalyst is filtered off, if appropriate freed from the solvent in vacuo, and the products of the formula I obtained are purified by distillation or recrystallization.

Die erfindungsgemäßen Verbindungen der Formel können gegebenenfalls in verschiedenen geometrischen Isomeren vorliegen, die in unterschiedlichen Mengenverhältnissen anfallen können. Außerdem liegen sie jeweils als optische Isomere vor. Dabei kann der Fall auftreten, daß bestimmte Isomere eine größere Wirksamkeit als andere aufweisen, so daß es gegebenenfalls zweckmäßig ist, die aktivere Komponete herzustellen bzw. zu isolieren, Sämtliche Isomeren werden erfindungsgemäß beansprucht.The compounds of the formula according to the invention can optionally be present in different geometric isomers which can be obtained in different proportions. They are also available as optical isomers. In this case, it can occur that certain isomers have a greater activity than others, so that it may be expedient to prepare or isolate the more active components. All the isomers are claimed according to the invention.

Als Beispiele für besonders wirksame Vertreter der erfindungsgemäßen Wirkstoffe seien außer der Herstellungsbeispielen und den Beispielen der Tabelle 1 genannt:

  • 2-Benzyloxymethyl-5-methyl-tetrahydrofur.an
  • 2-(2-Fluorbenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-5-methyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-methyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-methyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-äthyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-äthyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-propyl-tetrahydrofuran n
  • 2-(2-Fluorbenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-propyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2,5,5-trimethyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2,5,5-trimethyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2,5,5-trimethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2,5,5-trimethyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2,5,5-trimethyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2,5,5-trimethyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-äthyl-5,5-dimethyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-propyl-5,5-dimethyl-tetrahydrofuran n
  • 2-(2-Fluorbenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofura
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-phenyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-phenyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-äthyl-5-phenyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2,5-diäthyl-5-methyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-5-chlormethyl-tetrahydrofuran
  • 2-Benzyloxymethyl-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2-methyl-5-phenyl-tetrahydrofuran
  • 2-Benzyloxymethyl-5-äthyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-5-äthyl-tetrahydrofura
  • 2-(2-Methylbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-äthyl-tetrahydrofura
  • 2-(2,6-Dichlorbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 2-(Benzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2-(Benzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(2-Chlorbenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran n
  • 2-(4-Fluorbenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-2,5-dimethyl-5-äthyl-tetrahydrofuran
  • 2-(Benzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(2-Fluorbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran n
  • 2-(2-Chlorbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-5-methoxymethyl-tetrahydrofura
  • 2-(2-Methylbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(Benzyloxymethyl)-5-chlormethyl-tetrahydrofuran
Examples of particularly effective representatives of the active compounds according to the invention include the preparation examples and the examples in Table 1:
  • 2-Benzyloxymethyl-5-methyl-tetrahydrofur.an
  • 2- (2-fluorobenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -5-methyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-methyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-methyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-ethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-ethyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-propyl-tetrahydrofuran n
  • 2- (2-fluorobenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-propyl-tetrahydrofuran
  • 2-benzyloxymethyl-2,5,5-trimethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2,5,5-trimethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2,5,5-trimethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2,5,5-trimethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2,5,5-trimethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2,5,5-trimethyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-ethyl-5,5-dimethyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-propyl-5,5-dimethyl-tetrahydrofuran n
  • 2- (2-fluorobenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofura
  • 2- (2,6-dichlorobenzyloxymethyl) -2-propyl-5,5-dimethyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-phenyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-phenyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-ethyl-5-phenyl-tetrahydrofuran
  • 2-benzyloxymethyl-2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2,5-diethyl-5-methyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -5-chloromethyl-tetrahydrofuran
  • 2-benzyloxymethyl-2-methyl-5-phenyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2-methyl-5-phenyl-tetrahydrofuran
  • 2-benzyloxymethyl-5-ethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -5-ethyl-tetrahydrofura
  • 2- (2-methylbenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-ethyl-tetrahydrofura
  • 2- (2,6-dichlorobenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 2- (benzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2,5-dimethyl-5-vinyl-tetrahydrofuran
  • 2- (benzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (2-chlorobenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran n
  • 2- (4-fluorobenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -2,5-dimethyl-5-ethyl-tetrahydrofuran
  • 2- (benzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (2-fluorobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran n
  • 2- (2-chlorobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -5-methoxymethyl-tetrahydrofura
  • 2- (2-methylbenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (benzyloxymethyl) -5-chloromethyl-tetrahydrofuran

Die erfindungsgemäßen Wirkstoffe beeinflussen das Pflanzenwachstum und können deshalb als Defoliants, Desiccants, Krautabtötungsmittel, Keimhemmungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden. Unter Unkraut im weitesten Sinne sind alle Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selektive Herbizide wirken, hängt im wesentlichen von der angewendeten Menge ab.The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are all plants that 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.

Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden: Dikotyle Unkräuter der Gattungen: Senf (Sinapsis), Kresse (Lepidium), Labkraut (Galium), Sternmiere (Stellaria), Kamille (Matricaria), Hundskamille (Anthemis), Knopfkraut (Galinsoga), Gänsefuß (Chenopodium), Brennessel (Urtica), Kreuzkraut (Senecio), Fuchsschwanz (Amaranthus), Portulak (Portulaca), Spitzklette (Xanthium), Winde (Convolvulus), Prunkwinde (Ipomoea), Knöterich (Polygonum), Sesbanie (Sesbania), Ambrosie (Ambrosia), Kratzdistel (Cirsium), Distel (Carduus), Gänsedistel (Sonchus), Nachtschatten (Solanum), Sumpfkresse (Rorippa), Rotala, Büchsenkraut (Lindernia), Taubnessel (Lamium), Ehrenpreis (Veronica), Schönmalve (Abutilon), Emex, Stechapfel (Datura), Veilchen (Viola), Hanfnessel, Hohlzahn (Galeopsis), Mohn (Papaver), Flockenblume (Centaurea).
Dicotyle Kulturen der Gattungen: Baumwolle (Gossypium), Sojabohne (Glycine), Rübe (Beta), Mohre (Daucus), Gartenbohne (Phaseolus), Erbse (Pisum), Kartoffel (Solanum), Lein (Linum), Prunkwinde (Ipomoea), Bohne (Vicia), Tabak (Nicotiana), Tomate (Lycopersicon), Erdnuß (Arachis), Kohl (Brassica), Lattich (Lactuca), Gurke (Cucumis), Kürbis (Cuburbita).
Monokotyle Unkräuter der Gattungen: Hühnerhirse (Echinochloa), Borstenhirse (Setaria), Hirse (Panicum), Fingerhirse (Digitaria), Lieschgras (Phleum), Rispengras (Poa), Schwingel (Festuca), Eleusine, Brachiaria, Lolch (Lolium), Trespe (Bromus), Hafer (Avena), Zypergras (Cyperus), Mohrenhirse (Sorghum), Quecke (Agropyron), Hundszahngras (Cynodon), Monocharia, Fimbristylis, Pfeilkraut (Sagittaria), Sumpfried (Eleocharis), Simse (Scirpus), Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Straußgras (Agrostis), Fuchsschwanzgras (Alopecurus), Windhalm (Apera).
Monokotyle Kulturen der Gattungen: Reis (Orzya), Mais (Zea), Weizen (Triticum), Gerste (Hordeum), Hafer (Avena), Roggen (Secale), Mohrenhirse (Sorghum), Hirse (Panicum), Zuckerrohr (Saccharum), Ananas (Ananas), Spargel (Asparagus), Lauch (Allium).The active compounds according to the invention can be used, for example, in the following plants: dicotyledon weeds of the genera: mustard (Sinapsis), cress (Lepidium), bedstraw (Galium), starwort (Stellaria), chamomile (Matricaria), dog chamomile (Anthemis), button herb (Galinsoga ), Goose foot (Chenopodium), nettle (Urtica), ragwort (Senecio), foxtail (Amaranthus), purslane (Portulaca), Norway burdock (Xanthium), winch (Convolvulus), morning glory (Ipomoea), knotweed (Polygonum), sesbanie (Sesbania ), Ambrosia (Ambrosia), Thistle (Cirsium), Thistle (Carduus), Goose Thistle (Sonchus), Nightshade (Solanum), Marsh Cress (Rorippa), Rotala, Ciderweed (Lindernia), Deadnettle (Lamium), Honorary Award (Veronica), Green Mallow (Abutilon), Emex, Thorn Apple (Datura), Violet (Viola), Hemp Nettle, Hollow Tooth (Galeopsis), Poppy (Papaver), Knapweed (Centaurea).
Dicotyle cultures of the genera: Cotton (Gossypium), soybean (Glycine), turnip (Beta), Mohre (Daucus), haricot bean (Phaseolus), pea (Pisum), potato (Solanum), flax (Linum), morning glory (Ipomoea), Bean (Vicia), Tobacco (Nicotiana), Tomato (Lycopersicon), Peanut (Arachis), Cabbage (Brassica), Cos (Lactuca), Cucumber (Cucumis), Pumpkin (Cuburbita).
Monocotyledon weeds of the genera: Chicken millet (Echinochloa), Bristle millet (Setaria), Millet (Panicum), Finger millet (Digitaria), Lieschgras (Phleum), panicle grass (Poa), fescue (Festuca), Eleusine, Brachiaria, Lolch (Lolch (Lolch (Bromus), oat (Avena), cyper grass (Cyperus), black millet (Sorghum), grasshopper (Agropyron), canine grass (Cynodon), monocharia, fimbristylis, arrow herb (Sagittaria), swamp (Eleocharis), cornices (Scirpus), Paspalum Ischaemum, Sphenoclea, Dactyloctenium, ostrich grass (Agrostis), foxtail grass (Alopecurus), wind straw (Apera).
Monocot crops of the genera: Rice (Orzya), Maize (Zea), Wheat (Triticum), Barley (Hordeum), Oats (Avena), Rye (Secale), Black Millet (Sorghum), Millet (Panicum), Sugar Cane (Saccharum), Pineapple (pineapple), asparagus (asparagus), leek (allium).

Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen z.B. Forst-, Ziergehölz-, Obst-, Wein-, Citrus-, Nuss-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden.Depending on the concentration, the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops can e.g. Forestry, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.

Die erfindungsgemäßen Wirkstoffe weisen insbesondere starke herbizide Wirkungen gegen Gräser auf, ohne verschiedene Kulturpflanzen zu schädigen. Die können deshalb vorzugsweise zur selektiven Ungräserbekämpfung eingesetzt werden. Als Kulturen kommen insbesondere infrage: Rüben, Sojabohnen, Bohnen, Baumwolle, Raps, Erdnüsse, Gemüse, Mais und Reis.The active compounds according to the invention have, in particular, strong herbicidal effects against grasses, without damaging various crop plants. They can therefore preferably be used for selective weed control. The following crops are particularly suitable: beets, soybeans, beans, cotton, rapeseed, peanuts, vegetables, corn and rice.

Die erfindungsgemäßen Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigen Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Dichlordifluormethan oder Trichlorfluormethan; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-FettsäureEster, Polyoxyäthylen-Fettalkohol-Ather, z.B. Alkylaryl-polyglycol-Äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Lignin - Sulfitablaugen und Methylcellulose.The active compounds according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, 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; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; non-ionic 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; as dispersing agents: eg lignin sulfite liquor and methyl cellulose.

Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen zur Verstärkung und Ergänzung ihres Wirkungsspektrums je nach beabsichtigter Verwendung mit anderen herbiziden Wirkstoffen kombiniert werden, wobei Fertigformulierung oder Tankmischung möglich ist.The active compounds according to the invention, as such or in their formulations for strengthening and supplementing their spectrum of action, can be combined with other herbicidal active compounds, depending on the intended use, finished formulations or tank mixes being possible.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 Gewichtsprozent.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90 percent by weight.

Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder der daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Spritzen, Sprühen, Stäuben, Streuen und Gießen.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, dusting, scattering and pouring.

Die erfindungsgemäßen Wirkstoffe können sowohl nach als auch insbesondere vor dem Auflaufen der Pflanzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden.The active compounds according to the invention can be applied both after and in particular before the plants emerge. They can also be worked into the soil before sowing.

Die aufgewandte Wirkstoffmenge kann in größeren Bereichen schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effekts ab. Im allgemeinen liegen die Aufwandmengen zwischen 0,1 und 10 kg Wirkstoff pro ha, vorzugsweise zwischen 0,2 und 6 kg/ha.The amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect you want. In general, the application rates are between 0.1 and 10 kg of active ingredient per ha, preferably between 0.2 and 6 kg / ha.

Die erfindungsgemäßen Wirkstoffe besitzen nicht nur herbizide Eigenschaften, sondern darüberhinaus auch eine fungizide und insektizide Wirksamkeit.The active compounds according to the invention not only have herbicidal properties, but also a fungicidal and insecticidal activity.

Die guten herbiziden Wirkungen der erfindungsgemäßen Wirkstoffe und ihre selektiven Einsatzmöglichkeiten gehen aus den nachfolgenden Beispielen hervor.The good herbicidal effects of the active compounds according to the invention and their selective uses are evident from the examples below.

Beispiel AExample A Pre-emergence-TestPre-emergence test

  • Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
  • Emulgator: 1 Gewichtsteil AlkylarylpolyglycolätherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of 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.

Samen der Testpflanzen werden in normalen Boden ausgesät und nach 24 Stunden mit der Wirkstoffzubereitung begossen. Dabei hält man die Wassermenge pro Flächeneinheit zweckmäßigerweise konstant. Die Wirkstoffkonzentration in der Zubereitung spielt keine Rolle, entscheidend ist nur die Aufwandmenge des Wirkstoffs pro Flächeneinheit. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten:

  • 0% = keine Wirkung (wie unbehandelte Kontrolle)
  • 100% = totale Vernichtung
Seeds of the test plants are sown in normal soil and watered with the preparation of active compound after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
  • 0% = no effect (like untreated control)
  • 100% = total annihilation

Wirkstoffe, Aufwandmengen und Resultate gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0017
Active ingredients, application rates and results are shown in the table below:
Figure imgb0017

Herstellungsbeispiele Beispiel 1Production Examples Example 1 Beispiel 1example 1

Figure imgb0018
Figure imgb0018

(Verfahrenzvariante a)(Process variant a)

Zu einem Gemisch von 4,8 g (0,2 Mol) Natriumhydrid (6,0 g 80%iges Natriumhydrid in Paraffinöl) in 200 ml absolutem Dioxan werden bei Raumtemperatur unter Rühren 20,4 g (0,2 Mol) Tetrahydrofurfurylalkohol zugetropft. Man erhitzt danach noch 30 Minuten unter Rückfluß, kühlt auf 50°C ab und tropft dann zu dem so erhaltenen Natriumsalz 38 g (0,2 Mol) 2-Fluorbenzylbromid zu. Anschließend erhitzt man noch 3 Stunden unter Rückfluß, läßt auf Raumtemperatur abkühlen, versetzt zur Zerstörung von überschüssigem Natriumhydrid mit 20 ml Methanol und engt durch Abdestillieren des Lösungsmittels im Vakuum ein. Der Rückstand wird in 200 ml Wasser aufgenommen und mit Methylenchlorid extrahiert. Die organische Phase wird über Natriumsulfat getrocknet, filtriert, das Lösungsmittel abgezogen und der Rückstand im Vakuum fraktioniert. Man erhält 37,8 g (90% der Theorie) 2-(2-Fluor- benzyloxymethyl)-tetrahydrofuran vom Siedepunkt 79°C/0,1 mm.20.4 g (0.2 mol) of tetrahydrofurfuryl alcohol are added dropwise at room temperature to a mixture of 4.8 g (0.2 mol) of sodium hydride (6.0 g of 80% sodium hydride in paraffin oil) in 200 ml of absolute dioxane with stirring. The mixture is then refluxed for a further 30 minutes, cooled to 50 ° C. and 38 g (0.2 mol) of 2-fluorobenzyl bromide are then added dropwise to the sodium salt thus obtained. The mixture is then heated under reflux for 3 hours, allowed to cool to room temperature, mixed with 20 ml of methanol to destroy excess sodium hydride and concentrated by distilling off the solvent in vacuo. The residue is taken up in 200 ml of water and extracted with methylene chloride. The organic phase is dried over sodium sulfate, filtered, the solvent is stripped off and the residue is fractionated in vacuo. 37.8 g (90% of theory) of 2- (2-fluorobenzyloxymethyl) tetrahydrofuran with a boiling point of 79 ° C./0.1 mm are obtained.

Beispiel 2Example 2

Figure imgb0019
Figure imgb0019

(Verfahrensvariante d)(Process variant d)

25 g (0,1 Mol) 2-[ 1-(2-Chlorbenzyloxy)-propyl]-furan werden in 200 ml Methanol gelöst und nach Zugabe von 5 g Rhodium-Katalysator (5% Rhodium auf Aluminiumoxid) 4 Stunden bei 5 atü und Raumtemperatur hydriert. Danach wird der Katalysator abfiltriert, das Filtrat durch Abdestillieren des Lösungsmittels im Vakuum eingeengt und der Rückstand fraktioniert im Vakuum destilliert. Man erhält 15,7 g (62% der Theorie) 2-[1-(2-Chlorbenzyloxy)-propyl]-tetrahydrofuran vom Siedepunkt 101-105°C/0,1 mm.25 g (0.1 mol) of 2- [1- (2-chlorobenzyloxy) propyl] furan are dissolved in 200 ml of methanol and after the addition of 5 g of rhodium catalyst (5% rhodium on aluminum oxide) for 4 hours at 5 atm and hydrogenated at room temperature. The catalyst is then filtered off, the filtrate is concentrated by distilling off the solvent in vacuo and the residue is fractionally distilled in vacuo. 15.7 g (62% of theory) of 2- [1- (2-chlorobenzyloxy) propyl] tetrahydrofuran with a boiling point of 101-105 ° C./0.1 mm are obtained.

In analoger Weise können die in der nachfolgenden Tabelle 1 aufgeführten Verbindungen hergestellt werden.

Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
 The compounds listed in Table 1 below can be prepared in an analogous manner.
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025

Herstellung von AusgangsproduktenManufacture of raw materials

(a) Das gemäß Beispiel 2 als Ausgangsprodukt eingesetzte 2-[1-(2-Chlorbenzyloxy)-propyl]-furan kann wie folgt hergestellt werden:(a) The 2- [1- (2-chlorobenzyloxy) propyl] furan used as the starting product according to Example 2 can be prepared as follows:

Zu einem Gemisch von 4,8 g (0,2 Mol) Natriumhydrid (6,0 g 80%iges Natriumhydrid in Paraffinöl) und 200 ml absolutem Dioxan werden bei Raumtemperatur 27,2 g (0,2 Mol) 2-(1-Hydroxypropyl)-furan zugetropft.To a mixture of 4.8 g (0.2 mol) of sodium hydride (6.0 g of 80% sodium hydride in paraffin oil) and 200 ml of absolute dioxane, 27.2 g (0.2 mol) of 2- (1- Hydroxypropyl) furan added dropwise.

Man erhitzt danach 30 Min. unter Rückfluß, kühlt auf 50°C ab und tropft dann zu dem so erhaltenen Natriumsalz 32 g (0,2 Mol) 2-Chlorbenzylchlorid zu. Anschließend erhitzt man noch 3 Stunden unter Rückfluß, versetzt zur Zerstörung von überschüssigem Natriumhydrid mit 20 ml Methanol und engt durch Abdestillieren des Lösungsmittels im Vakuum ein.The mixture is then heated under reflux for 30 minutes, cooled to 50 ° C. and 32 g (0.2 mol) of 2-chlorobenzyl chloride are then added dropwise to the sodium salt thus obtained. The mixture is then heated under reflux for a further 3 hours, 20 ml of methanol are added to destroy excess sodium hydride and the mixture is concentrated by distilling off the solvent in vacuo.

Der Rückstand wird in 200 ml Wasser aufgenommen und mit Methylenchlorid extrahiert. Die organische Phase wird über Natriumsulfat getrocknet, filtriert, das Lösungsmittel abgezogen und der Rückstand im Vakuum fraktioniert. Man erhält 36,0 g (72% d. Th.) 2-[1-(2-Chlorbenzyloxy)-propyl]-furan vom Siedepunkt 95-97°C/0,1 mm. Hg.The residue is taken up in 200 ml of water and extracted with methylene chloride. The organic phase is dried over sodium sulfate, filtered, the solvent is stripped off and the residue is fractionated in vacuo. 36.0 g (72% of theory) of 2- [1- (2-chlorobenzyloxy) propyl] furan with a boiling point of 95-97 ° C./0.1 mm are obtained. Ed.

Claims (5)

1. Tetrahydrofurane derivatives of the formula I
Figure imgb0042
in which
R1 to R6 are identical or different and represent hydrogen, straight-chain or branched C1_6 alkyl, C1_2 halogenalkyl with up to three identical or different halogen atoms, alkoxyalkyl with 1 or 2 C atoms in each alkyl part, as well as phenyl or benzyloxyalkyl with 1 or 2 C atoms in the alkyl part each optionally substituted by halogen, C1_2 alkyl, C1_2 alkoxy or C1_2 halogenoalkyl with up to three identical or different halogen atoms,
R5 and R6 together also represent a saturated carboxylic ring with altogether 3 to 6 C atoms,
R7 represents hydrogen, straight-chain or branched C1_6 alkyl, C3-6 cycloalkyl, C2-4 alkenyl, C2_4 alkinyl, alkoxyalkyl with 1 to 2 C atoms in each alkyl part, as well as phenyl or benzyloxyalkyl with 1 or 2 C atoms in the alkyl part each substituted by halogen, C1_2 alkyl, C1_2 alkoxy, or C1_2 halogenoalkyl with up to three identical or different halogen atoms,
R6 and R9 are identical or different and represent hydrogen, straight-chain or branched C1_6 alkyl, C2_4 alkenyl, C2_4 alkinyl, C3_6 cycloalkyl, C1_4 alkoxy, as well as phenyl, benzyl or benzyloxy each optionally substituted by halogen, C1_2 alkyl, C1_2 alkoxy or C1_2 halogenoalkyl with up to three identical or different halogen atoms,
R10 represents hydrogen, straight-chain or branched C1_6 alkyl, C2_4 alkenyl, C2_4 alkinyl, C1_2 halogenoalkyl with up to three identical or different halogen atoms, as well as phenyl optionally substituted by halogen, C1_2 alkyl, C1_2 alkoxy or C1_2 halogenoalkyl with up to three identical or different halogen atoms and
Y represents optionally substituted aryl with 6 to 10 C atoms, which can carry one or more identical or different substituents from the following: the halogens fluorine, chlorine or bromine; alkyl and alkoxy with in each case 1 to 4 C atoms; halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case up to 4 C atoms and up to 5 halogen atoms; phenyl, phenoxy or phenoxycarbonyl optionally substituted by halogen, alkyl and alkoxy with in each case 1 to 2 C atoms as well as halogenalkyl with up to 1 C atoms and up to 3 identical or different halogen atoms as well as halogenoalkyl with up to 1 C atoms and up to 3 identical or different halogen the tri-, tetra- or penta-methylene radical; with the proviso that if Y represents phenyl this must be substituted if R1 to R10 denote hydrogen.
2. Process for the preparation of tetrahydrofurane derivatives of the formula (I), characterised in that
a) alcoholates of 2-hydroxymethyl-tetrahydrofurane derivatives of the formula
Figure imgb0043
in which
RI to R9 have the meaning indicated above and
M represents an alkali metal or alkaline earth metal,
are reacted with a compound of the formula
Figure imgb0044
in which
R10 and Y have the meaning indicated above and
Z represents halogen, or the mesylate or tosylate radical,
in a manner known per se optionally in the presence of a diluent, or in that
b) diols of the formula
Figure imgb0045
in which
R1 to R10 and Y have the meaning indicated above,

are heated in a manner known per se in the presence of an acid catalyst and optionally in the presence of a diluent; or in that
(c) those compounds of the formula (I) in which either RI and R7 or RI and R4 or R4 and R5 represent hydrogen are obtained when dihydrofurane derivatives of the formulae
Figure imgb0046
Figure imgb0047
and/or
Figure imgb0048
in which
R1 to R10 and Y have the meaning indicated above,

are hydrogenated with hydrogen, in a manner known per se in the presence of a catalyst and optionally in the presence of a diluent; or in that
d) those compounds of the formula (I) in which R1, R4, R5 and R7 represent hydrogen, are obtained when furane derivatives of the formula
Figure imgb0049
in which
R2, R3, R6, R8, R9, R10 and Y have the meaning indicated above,

are hydrogenated with hydrogen, in a manner known per se, in the presence of a catalyst and optionally in the presence of a diluent.
3. Herbicidal agents, characterised in that they contain tetrahydrofurane derivatives according to Claim 1.
4. Use of tetrahydrofurane derivatives according to Claim 1 for combating undesired plant growth.
5. Process for the preparation of herbicidal agents, characterised in that tetrahydrofurane derivatives according to Claim 1 are mixed with extenders and/or surface-active agents.
EP78100007A 1977-06-01 1978-06-01 Tetrahydrofurane derivatives, processes for their preparation and their use as herbicides Expired EP0000002B1 (en)

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DE2724675 1977-06-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3982114A1 (en) 2020-10-06 2022-04-13 Eitel, Veronika Holder for an object to be examined
EP4063016A1 (en) 2021-03-25 2022-09-28 Verein zur Förderung von Innovationen durch Forschung, Entwicklung und Technologietransfer e.V. (Verein INNOVENT e.V.) Atomizing nozzle

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4289884A (en) * 1979-01-08 1981-09-15 Shell Oil Company Herbicidal tetrahydrofuran derivatives
US4400198A (en) * 1980-01-21 1983-08-23 Shell Oil Company Herbicidal tetrahydrofuran derivatives
CA1152510A (en) * 1980-01-21 1983-08-23 Shell Canada Limited Unsaturated alcohols and their use in the preparation of oxolanes
US4356023A (en) 1980-06-30 1982-10-26 Shell Oil Company Certain herbicidal tetrahydrofurans
DE3271239D1 (en) * 1981-05-01 1986-06-26 Shell Int Research Substituted tetrahydrofuran herbicides
US4670041A (en) * 1981-12-16 1987-06-02 E. I. Du Pont De Nemours And Company Oxabicycloalkane herbicides
US4493936A (en) * 1982-06-14 1985-01-15 Shell Oil Company 2-Cyano-tetrahydrofuran-5-methanols
US4439225A (en) * 1982-06-14 1984-03-27 Shell Oil Company Herbicidal cyano-tetrahydrofuranylmethyl ether and cyano-tetrahydropyranylmethyl ether derivatives
US4579582A (en) * 1982-08-18 1986-04-01 Chevron Research Company 5-deoxy-3-O-arylmethyl or substituted arylmethyl-1,2-O-alkylidene-α-D-xylofuranose herbicide derivatives
US4594094A (en) * 1983-04-04 1986-06-10 Shell Oil Company Oxacycloalkane-alpha-(thio)carboxylic acid derivatives and use as plant growth regulators and herbicides
US4497649A (en) * 1983-08-18 1985-02-05 Chevron Research Company 5-O-Acyl-5-C-alkyl-3-O-arylmethyl or substituted arylmethyl-1,2-O-alkylidene-αD-gluco-pentofuranose and β-L-ido-pentofuranose herbicides
US4725302A (en) * 1984-11-27 1988-02-16 Ciba-Geigy Corporation Substituted phenylhydrazines and phenyloxadiazolinones and pesticidal usage thereof
JPS6234626A (en) * 1985-08-06 1987-02-14 Kawasaki Steel Corp Manufacture of electric welded pipe
DE3628287A1 (en) * 1986-08-20 1988-02-25 Erlau Ag Eisen Drahtwerk TIRE CHAIN
IT1197873B (en) * 1986-10-15 1988-12-21 Erba Farmitalia PROCEDURE FOR THE PREPARATION OF AZETIDINONES
AT392238B (en) * 1987-04-16 1991-02-25 Jenbacher Werke Ag Device for controlling compressed-air-controlled brakes on rail vehicles
AT387931B (en) * 1987-08-13 1989-04-10 Iag Ind Automatisierungsges M Hot press for producing disc-brake pads
AT397333B (en) * 1988-06-20 1994-03-25 Elin Union Ag Device for fixing components
AT390413B (en) * 1988-07-20 1990-05-10 Steinbach Gerhard Ludwig Self-adhesive film for motor-vehicle bodies
AT399414B (en) * 1989-03-21 1995-05-26 Rudolf Dipl Ing Winkler Distance measuring device for motor vehicles
AT396897B (en) * 1990-12-21 1993-12-27 Haltmeier Georg Agent for impregnating wood
AT399074B (en) * 1991-12-23 1995-03-27 Lenhard Ges M B H DEVICE FOR HOLDING BOARD
AT398158B (en) * 1992-07-16 1994-10-25 Attrezzature Meccanismi Minute Tensioning device
AT398199B (en) * 1992-11-27 1994-10-25 Chemie Linz Gmbh METHOD FOR PRODUCING ARYLHYDANTOINES
US7295509B2 (en) 2000-09-13 2007-11-13 Qualcomm, Incorporated Signaling method in an OFDM multiple access system
FR2873555B1 (en) * 2004-07-28 2008-04-18 Compin Sa SEAT FOR PUBLIC TRANSPORT VEHICLE
DK2254549T4 (en) 2008-03-17 2019-07-22 Alcon Res Ltd AURAL PHARMACEUTICAL COMPOSITIONS, CONTAINING BORATE-POLYOL COMPLEXES
EP3201724A4 (en) 2014-09-30 2018-05-16 Hewlett-Packard Development Company, L.P. Gesture based manipulation of three-dimensional images
WO2024108053A1 (en) 2022-11-17 2024-05-23 Sanofi Ceacam5 antibody-drug conjugates and methods of use thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7712227A (en) * 1976-11-08 1978-05-10 Inco Europ Ltd METHOD OF STORAGE OF HYDROGEN WHICH CAN BE RELEASED LATER.

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1370678A (en) * 1962-06-29 1964-08-28 Shell Res Ltd Molluscicidal derivatives of dimethyl ether
GB1591093A (en) * 1976-11-10 1981-06-17 Shell Int Research 2-benzyloxymethylfuran derivatives and their use as herbicides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7712227A (en) * 1976-11-08 1978-05-10 Inco Europ Ltd METHOD OF STORAGE OF HYDROGEN WHICH CAN BE RELEASED LATER.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3982114A1 (en) 2020-10-06 2022-04-13 Eitel, Veronika Holder for an object to be examined
EP4063016A1 (en) 2021-03-25 2022-09-28 Verein zur Förderung von Innovationen durch Forschung, Entwicklung und Technologietransfer e.V. (Verein INNOVENT e.V.) Atomizing nozzle

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EP0000002A1 (en) 1978-12-20
JPS543057A (en) 1979-01-11
IL54802A0 (en) 1978-07-31
IT7823999A0 (en) 1978-05-30
PT68098A (en) 1978-06-01
BR7803476A (en) 1979-02-20
DD137320A5 (en) 1979-08-29
ZA783090B (en) 1979-06-27
DE2860975D1 (en) 1981-11-19
DE2724675A1 (en) 1978-12-14
DK242578A (en) 1978-12-02

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