EP0000002A1 - 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
EP0000002A1
EP0000002A1 EP78100007A EP78100007A EP0000002A1 EP 0000002 A1 EP0000002 A1 EP 0000002A1 EP 78100007 A EP78100007 A EP 78100007A EP 78100007 A EP78100007 A EP 78100007A EP 0000002 A1 EP0000002 A1 EP 0000002A1
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EP
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Prior art keywords
tetrahydrofuran
alkyl
phenyl
atoms
optionally substituted
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EP78100007A
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German (de)
French (fr)
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EP0000002B1 (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 present invention relates to new 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- (l'-methyl-2'-methoxyethyl) chloroacetanilide
  • DT-OS 2 328 340 grass-like weeds
  • 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, and also have a significantly better action Selectivity in important crops.
  • the active compounds according to the invention thus represent a substantial enrichment of the herbicidal compositions, in particular the grass herbicides.
  • Formula (II) provides a general definition of the alcoholates of 2-hydroxymethyl tetrahydrofuran derivatives to be used as starting materials for process variant (a).
  • R 1 to R different 6 same or different and preferably represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, halogenoalkyl with up same to 2 carbon atoms and up to three or different halogen atoms, preferred halogens being fluorine, chlorine and bromine, alkoxyalkyl having 1 or 2 carbon atoms in each alkyl part, and optionally substituted phenyl and benzyloxyalkyl having 1 to 2 carbon atoms in the alkyl part, the preferred substituents being: halogen, alkyl and alkoxy each having 1 or 2 carbon atoms and haloalkyl up to 2 carbon atoms and up to three identical or different halogen atoms, such as in particular fluorine and chlorine.
  • R 'and R 6 also preferably together represent a
  • R 7 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxyalkyl having 1 or 2 carbon atoms in each alkyl part and optionally substituted phenyl and benzyloxyalkyl with 1 to 2 carbon atoms in the alkyl part, the substituents which are preferably those already mentioned for R 'to R 6 .
  • R 8 and R 9 are the same or different and are preferably hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and for optionally substituted phenyl, benzyl or benzyloxy, preferably as the substituents in question preferably already mentioned for R 1 to R. 6
  • M preferably represents the alkali metals sodium and potassium as well as for 1 equivalent of the alkaline earth metals magnesium and calcium.
  • 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-hydroxymethyl-tetrahydrofuran 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) provides a general definition of the compounds to be used as starting materials for process variant (a).
  • R 10 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, haloalkyl having up to 2 carbon and up to three identical or different halogen atoms, the halogens in particular Fluorine, chlorine and bromine as well as optionally substituted phenyl, the substituents which are preferably those which are preferably mentioned at R 'to R 6 in the starting materials of the formula (II).
  • Y preferably represents optionally substituted aryl having 6 to 10 carbon atoms, in particular phenyl and naphthyl, which can carry one or more identical or different substituents.
  • Preferred substituents are the halogens fluorine, chlorine or bromine; Alkyl and alkexy of 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio with up to 4 carbon atoms and up to 5 halogen atoms, in particular with up to 2 carbon atoms and up to 3 identical or different halogen atoms, halogen, in particular fluorine, chlorine and bromine; phenyl, phenoxy or phenoxycarbonyl optionally substituted by halogen, in particular fluorine, chlorine or bromine, alkyl and alkoxy each having 1 to 2 carbon atoms and haloalkyl having up to 2 carbon and up to 3 identical or different halogen atoms, such as in particular fluorine and chlorine; Alk
  • Formula (IV) provides a general definition of the diols to be used as starting materials for process variant (b).
  • R 'to R 9 preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II).
  • R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the compounds of the formula (III).
  • R 'to R' preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II).
  • R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the compounds of the formula (III).
  • Formula (VI) provides a general definition of the furan derivatives to be used as starting materials for process variant (d).
  • R 2 , R 3 , R ', R 5 and R 9 preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II).
  • R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the halides of the formula (III).
  • the alcoholates of the formulas (VIIa), (VIIb), (VIIc) and (VIII) are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyl-dihydrofuran 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 also known or can be prepared by known methods (see, inter alia, H. Kröper in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, pp. 519ff (1965) and the one cited therein Literature).
  • 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. In general, 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 advantageously carried out in such a way that a 2-hydroxymethyl-tetrahydrofuran derivative is used, the latter converted into the alkali metal alcoholate of the formula (II) in a suitable inert solvent using alkali metal hydride or amide, and the latter without Isolation is immediately reacted with a compound of the formula (III) and the compounds of the formula (I) according to the invention are thus obtained 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 a two-phase system, such as aqueous sodium or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer catalyst, such as, for example, ammonium or phosphonium compounds.
  • a phase transfer catalyst such as, for example, 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 then the water is 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).
  • I n generally 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 (I) 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. The case may arise that certain isomers have a greater activity than others, so that it may be expedient to prepare or isolate the more active components. All 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 understood to mean 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.
  • Monocot crops of the genera Rice (Oryza), 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 wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weeding. fighting 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 manufactured in a known manner, e.g. B. 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.
  • 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 also be used as auxiliary 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, e.g. B.
  • Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B.
  • 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; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • 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 formulation or tank mix 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 emergence of the plants. 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

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

Abstract

1. Tetrahydrofurane derivatives of the formula I see diagramm : EP0000002,P22,F6 in which R**1 to R**6 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, R**5 and R**6 together also represent a saturated carboxylic ring with altogether 3 to 6 C atoms, R**7 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, R**8 and R**9 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, R**10 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 R**1 to R**10 denote hydrogen.

Description

Die vorliegende Erfindung betrifft neue Tetrahydrofuran-Derivate, mehrere Verfahren zu ihrer Herstellung sowie ihre Verwendung als Herbizide, insbesondere als selektive Herbizide.The present invention relates to new 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-(l'-methyl-2'-methoxyäthyl)-chloracetanilid, als Herbizide, insbesondere zur Bekämpfung von grasartigen Unkräutern, verwendet werden können (vergleiche DT-OS 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- (l'-methyl-2'-methoxyethyl) chloroacetanilide, can be used as herbicides, in particular for controlling grass-like weeds (cf. DT-OS 2 328 340). However, the selectivity of these compounds is not always satisfactory.

Es wurden neue Tetrahydrofuran-Derivate der Formel

Figure imgb0001
in welcher

  • R1 bis R6 gleich oder verschieden sind und für Wasserstoff, Alkyl, Halogenalkyl, Alkoxyalkyl, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyloxyalkyl stehen,
  • R5und R6 auch gemeinsam für einen gesättigten carbocyclischen Ring stehen,
  • R? für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkoxyalkyl, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyloxyalkyl steht,
  • R8 und R9 gleich oder verschieden sind und für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkoxy, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyl und Benzyloxy stehen,
  • R10 für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Halogenalkyl oder gegebenenfalls substituiertes Phenyl steht und
  • Y für gegebenenfalls substituiertes Aryl steht, mit der Maßgabe, daß, falls Y für Phenyl steht, dieses substituiert sein muß, wenn R' bis R'0 Wasserstoff bedeuten, aufgefunden.
There were new tetrahydrofuran derivatives of the formula
Figure imgb0001
 in which
  • R 1 to R 6 are identical or different and represent hydrogen, alkyl, haloalkyl, alkoxyalkyl, optionally substituted phenyl or optionally substituted benzyloxyalkyl,
  • R 5 and R 6 together also represent a saturated carbocyclic ring,
  • R ? represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, optionally substituted phenyl or optionally substituted benzyloxyalkyl,
  • R 8 and R 9 are identical or different and represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, optionally substituted phenyl or optionally substituted benzyl and benzyloxy,
  • R 10 represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl or optionally substituted phenyl and
  • Y represents optionally substituted aryl, with the proviso that if Y represents phenyl, it must be substituted if R 'to R' 0 are hydrogen, found.

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

Weiterhin wurde gefunden, daß man die Tetrahydrofuran-Derivate der Formel (I) erhält, wenn man

  • (a) Alkoholate von 2-Hydroxymethyl-tetrahydrofuran-Derivaten der Formel
    Figure imgb0002
    in welcher
    • R1 bis R9 die oben angegebene Bedeutung haben und
    • M für ein Alkali- oder Erdalkalimetall steht,
    • mit einer Verbindung der Formel
      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,
    • gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man
  • (b) Diole der Formel
    Figure imgb0004
    in welcher
    • R1 bi s R10
    • und Y die oben angegebene Bedeutung haben,
    • in Gegenwart eines sauren Katalysators erhitzt und gegebenenfalls in Gegenwart eines Verdünnungsmittels erhitzt.
    • Verbindungen der Formel (I), in denen entweder R' und R7 oder R1 und R4 oder R4und R5 für Wasserstoff stehen, können auch erhalten werden, wenn man
  • (c) Dihydrofuran-Derivate der Formeln
    Figure imgb0005
    Figure imgb0006
    und/oder
    Figure imgb0007
     in welchen
    • R1 bis R10
    • und Y die oben angegebene Bedeutung haben,
    • in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert.
    • Verbindungen der Formel (I), in denen R1, R4, R5 und R7 für Wasserstoff stehen, können auch erhalten werden, wenn man
  • (d) Furan-Derivate der Formel
    Figure imgb0008
    in welcher
    • R2, R3, R6, R8,
    • R9, R10 und Y die oben angegebene Bedeutung haben,
    • in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert.
Furthermore, it was found that the tetrahydrofuran derivatives of the formula (I) are obtained when
  • (a) Alcoholates of 2-hydroxymethyl-tetrahydrofuran derivatives of the formula
    Figure imgb0002
     in which
    • R 1 to R 9 have the meaning given above and
    • M represents an alkali or alkaline earth metal,
    • with a compound of the formula
      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,
    • if appropriate in the presence of a diluent, or if one
  • (b) Diols of the formula
    Figure imgb0004
     in which
    • R 1 to R 10
    • and Y have the meaning given above,
    • heated in the presence of an acid catalyst and optionally heated in the presence of a diluent.
    • Compounds of formula (I) in which either R '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
    Figure imgb0005
    Figure imgb0006
     and or
    Figure imgb0007
     in which
    • R 1 to R 10
    • and Y have the meaning given above,
    • hydrogenated in the presence of a catalyst and optionally in the presence of a diluent with hydrogen.
    • Compounds of 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
    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 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)-chloracet- anilid, in der herbiziden Wirkung überlegen und zeigen außerdem eine deutlich bessere Selektivität in wichtigen Kulturpflanzen. 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, and also have a significantly better action Selectivity in important crops. The active compounds according to the invention thus represent a substantial enrichment of the herbicidal compositions, in particular the 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 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 für die Verfahrensvariante(a)als Ausgangsstoffe zu verwendenden Alkoholate von 2-Hydroxymethyl-tetrahydrofuran-Derivaten sind durch die Formel (II) allgemein definiert. In dieser Formel sind R1 bis R6 gleich oder verschieden und stehen vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu drei gleichen oder verschiedenen Halogenatomen, wobei als Halogene insbesondere Fluor, Chlor und Brom stehen, Alkoxyalkyl mit 1 oder 2 Kohlenstoffatomen in jedem Alkylteil, sowie für gegebenenfalls substituiertes Phenyl und Benzyloxyalkyl mit 1 bis 2 Kohelenstoffatomen im Alkylteil, wobei als Substituenten vorzugsweise infrage kommen: Halogen, Alkyl und Alkoxy mit jeweils 1 oder 2 Kohlenstoffatomen sowie Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu drei gleichen oder verschiedenen Halogenatomen, wie insbesondere Fluor und Chlor. R' und R6 stehen außerdem vorzugsweise gemeinsam für einen gesättigten carbocyclischen Ring mit insgesamt 3 bis 6 Kohlenstoffatomen.Formula (II) provides a general definition of the alcoholates of 2-hydroxymethyl tetrahydrofuran derivatives to be used as starting materials for process variant (a). In this formula, R 1 to R different 6 same or different and preferably represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, halogenoalkyl with up same to 2 carbon atoms and up to three or different halogen atoms, preferred halogens being fluorine, chlorine and bromine, alkoxyalkyl having 1 or 2 carbon atoms in each alkyl part, and optionally substituted phenyl and benzyloxyalkyl having 1 to 2 carbon atoms in the alkyl part, the preferred substituents being: halogen, alkyl and alkoxy each having 1 or 2 carbon atoms and haloalkyl up to 2 carbon atoms and up to three identical or different halogen atoms, such as in particular fluorine and chlorine. R 'and R 6 also preferably together represent a saturated carbocyclic ring with a total of 3 to 6 carbon atoms.

R7 steht vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, Cycloalkyl mit 3 bis 6 Kohlenstoffatomen, Alkenyl und Alkinyl mit jeweils 2 bis 4 Kohlenstoffatomen, Alkoxyalkyl mit 1 oder 2 Kohlenstoffatomen in jedem Alkylteil sowie für gegebenenfalls substituiertes Phenyl und Benzyloxyalkyl mit 1 bis 2 Kohlenstoffatomen im Alkylteil, wobei als Substituenten vorzugsweise die bei R' bis R6 bereits vorzugsweise genannten infrage kommen.R 7 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxyalkyl having 1 or 2 carbon atoms in each alkyl part and optionally substituted phenyl and benzyloxyalkyl with 1 to 2 carbon atoms in the alkyl part, the substituents which are preferably those already mentioned for R 'to R 6 .

R8 und R9 sind gleich oder verschieden und stehen vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, Cycloalkyl mit 3 bis 6 Kohlenstoffatomen, Alkenyl und Alkinyl mit jeweils 2 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen sowie für gegebenenfalls substituiertes Phenyl, Benzyl oder Benzyloxy, wobei als Substituenten vorzugsweise die bei R1 bis R6 bereits vorzugsweise genannten infrage kommen.R 8 and R 9 are the same or different and are preferably hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and for optionally substituted phenyl, benzyl or benzyloxy, preferably as the substituents in question preferably already mentioned for R 1 to R. 6

M steht vorzugsweise für die Alkalimetalle Natrium und Kalium sowie für 1 Äquivalent der Erdalkalimetalle Magnesium und Calcium.M preferably represents the alkali metals sodium and potassium as well as for 1 equivalent of the alkaline earth metals magnesium and calcium.

Die Alkoholate der Formel (II) sind bekannt oder lassen sich nach bekannten Methoden herstellen. 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 (vergleiche 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-hydroxymethyl-tetrahydrofuran 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 also known or can be prepared by known methods (see, inter alia, H. Kröper, in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, pp. 519ff (1965) and 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-(1-Hydroxyprop-1-yl)-tetrahydrofuran
  • 2-(1-Hydroxyäthyl)-tetrahydrofuran
  • 2-(3-Hydroxypent-3-yl)-terahydrofuran
  • 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- (1-hydroxyprop-1-yl) tetrahydrofuran
  • 2- (1-hydroxyethyl) tetrahydrofuran
  • 2- (3-hydroxypent-3-yl) terahydrofuran
  • 2- (hydroxyphenylmethyl) tetrahydrofuran
  • 2- (2-hydroxyprop-2-yl) tetrahydrofuran

Die weiterhin für die Verfahrensvariante(a) als Ausgangsstoffe zu verwendenden Verbindungen sind durch die Formel (III) allgemein definiert. In dieser Formel steht R10 vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, Alkenyl und Alkinyl mit jeweils 2 bis 4 Kohlenstoffatomen, Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu drei gleichen oder verschiedenen Halogenatomen, wobei als Halogene insbesondere Fluor, Chlor und Brom stehen, sowie für gegebenenfalls substituiertes Phenyl, wobei als Substituenten vorzugsweise die bei R' bis R6 bei den Ausgangsstoffe der Formel (II) bereits vorzugsweise genannten infrage kommen.Formula (III) provides a general definition of the compounds to be used as starting materials for process variant (a). In this formula, R 10 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, haloalkyl having up to 2 carbon and up to three identical or different halogen atoms, the halogens in particular Fluorine, chlorine and bromine as well as optionally substituted phenyl, the substituents which are preferably those which are preferably mentioned at R 'to R 6 in the starting materials of the formula (II).

Y steht vorzugsweise für gegebenenfalls substituiertes Aryl mit 6 bis 10 Kohlenstoffatomen, insbesondere für Phenyl und Naphthyl, die einen oder mehrere gleiche oder verschiedene Substituenten tragen können. Als Substituenten seien vorzugsweise genannt, die Halogene Fluor, Chlor oder Brom; Alkyl und Alkexy mit 1 bis 4 Kohlenstoffatomen; Halogenalkyl, Halogenalkoxy und Halogenalkylthio mit bis zu 4 Kohlenstoffatomen und bis zu 5 Halogenatomen, insbesondere mit bis zu 2 Kohlenstoff- 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 Kohlenstoffatomen sowie Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu 3 gleichen oder verschiedenen Halogenatomen, wie insbesondere Fluor und Chlor, substituiertes Phenyl, Phenoxy oder Phenoxycarbonyl; Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil; die Methylendioxo-Gruppe sowie der Tri-, Tetra- oder Pentamethylen-Rest. Für den Fall, daß Y für Phenyl steht, muß dieses substituiert sein, wenn R'bis R'0 Wasserstoff bedeuten.Y preferably represents optionally substituted aryl having 6 to 10 carbon atoms, in particular phenyl and naphthyl, which can carry one or more identical or different substituents. Preferred substituents are the halogens fluorine, chlorine or bromine; Alkyl and alkexy of 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio with up to 4 carbon atoms and up to 5 halogen atoms, in particular with up to 2 carbon atoms and up to 3 identical or different halogen atoms, halogen, in particular fluorine, chlorine and bromine; phenyl, phenoxy or phenoxycarbonyl optionally substituted by halogen, in particular fluorine, chlorine or bromine, alkyl and alkoxy each having 1 to 2 carbon atoms and haloalkyl having up to 2 carbon and up to 3 identical or different halogen atoms, such as in particular fluorine and chlorine; Alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part; the methylenedioxo group and the tri, tetra or pentamethylene radical. In the event that Y is phenyl, this must be substituted if R'bis R ' 0 are hydrogen.

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-Trifluoruethylbenzylchlorid, 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-Dioxomethylenbenzylchlorid, 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-fluorbenzylchlorid, 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-l-phenyl- äthan, 1-Brom-1-(2-fluorphenyl)-äthan, 1-Brom-1-(2-methylphenyl)-äthan.
The starting materials of the 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-methylbenzylchloride, 2-methoxybenzylchloride, 3-methoxybenzylchloride, 4-methoxybenzylchloride, 2-trifluoruethylbenzylchloride, 3-trifluoromethylbenzylchloride, 4-trifluoromethylbenzylchloride, 4-phenylbenzylchloride, 2,6-difluorobenzylchloride, 2,6-difluorobenzylchloride, 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-dioxomethylenebenzyl 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-l- 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. In dieser Formel stehen R' bis R9 vorzugsweise für die Reste, die bei den Alkoholaten der Formel (II) bereits vorzugsweise genannt wurden. R10 und Y stehen vorzugsweise für die Reste die bei den Verbindungen der Formel (III) bereits vorzugsweise genannt wurden.Formula (IV) provides a general definition of the diols to be used as starting materials for process variant (b). In this formula, R 'to R 9 preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II). R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the compounds of the formula (III).

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-penran-2,5-diol
  • 1-(2-Methylbenzyloxy)-5,5-dimethyl-pentan-2,5-diol
  • l-(2-Brombenzyloxy)-5,5-dimethyl-penatan-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-pentam-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-dimethyl-penran-2,5-diol
  • 1- (2-methylbenzyloxy) -5,5-dimethylpentan-2,5-diol
  • 1- (2-bromobenzyloxy) -5,5-dimethyl-penatan-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-pentam-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. In diesen Formeln stehen R' bis R' vorzugsweise für die Reste, die bei den Alkoholaten der Formel (II) bereits vorzugsweise genannt wurden. R10 und Y stehen vorzugsweise für die Reste, die bei den Verbindungen der Formel (III) bereits vorzugsweise genannt wurden.The formulas (Va), (Vb) and (Vc) generally define the dihydrofuran derivatives to be used as starting materials for process variant (c). In these formulas, R 'to R' preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II). R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the compounds of the formula (III).

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

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. However, they are obtained in a simple manner if, according to process variant (a), alcoholates of 2-hydroxymethyl-dihydrofuran derivatives of the formulas
Figure imgb0013
Figure imgb0014
Figure imgb0015
 in which
  • R 'to R9
  • 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. In dieser Formel stehen R2, R3, R', R5 und R9 vorzugsweise für die Reste, die bei den Alkoholaten der Formel (II) bereits vorzugsweise genannt wurden. R10 und Y stehen vorzugsweise für die Reste, die bei den Halogeniden der Formel (III) bereits vorzugsweise genannt wurden.Formula (VI) provides a general definition of the furan derivatives to be used as starting materials for process variant (d). In this formula, R 2 , R 3 , R ', R 5 and R 9 preferably represent the radicals which have already been mentioned as preferred for the alcoholates of the formula (II). R 10 and Y preferably represent the radicals which have already been mentioned as preferred for the halides of the formula (III).

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-furan-Derivaten der Formel

Figure imgb0016
in welcher

  • R2, R3, R6, R8,
  • R9 und M die oben angegebene Bedeutung haben,
  • mit einer Verbindung der Formel (III) gegebenenfalls in Gegenwart eines Verdünnungmittels 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
Figure imgb0016
 in which
  • R2, R 3 , R 6 , R8,
  • R 9 and M have the meaning given above,
  • with a compound of 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-Methylbenzyloxy)-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-Ea-(2-chlorbenzyloxy)-benzyl]-furan
  • 2-[2-(2-Fluorbenzyloxy)-prop-2-yl]-furan
  • 2-(α-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-methylbenzyloxy) 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-Ea- (2-chlorobenzyloxy) benzyl] furan
  • 2- [2- (2-fluorobenzyloxy) prop-2-yl] furan
  • 2- (α-phenylbenzyloxy-methyl) furan

Die Alkoholate der Formeln (VIIa), (VIIb), (VIIc) und (VIII)sind bekannt oder lassen sich nach bekannten Methoden herstellen. Man erhält sie z.B., indem man die entsprechenden 2-Hydroxymethyl-dihydrofuran-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 (vergleiche 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 (VIIa), (VIIb), (VIIc) and (VIII) are known or can be prepared by known methods. They are obtained, for example, by reacting the corresponding 2-hydroxymethyl-dihydrofuran 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 also known or can be prepared by known methods (see, inter alia, H. Kröper in Houben-Weyl, 'Methods of Organic Chemistry', Volume 6/3, pp. 519ff (1965) and the one cited therein Literature).

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 O 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 Reaktionsprodukt abdestilliert werden.In process variant (a), the reaction temperatures can be varied within a substantial range. In general, 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 (II) überführt, und letzteres ohne Isolierung sofort mit einer Verbindung der Formel (III) umsetzt und somit die erfindungsgemäßen Verbindungen der Formel (I) 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 advantageously carried out in such a way that a 2-hydroxymethyl-tetrahydrofuran derivative is used, the latter converted into the alkali metal alcoholate of the formula (II) in a suitable inert solvent using alkali metal hydride or amide, and the latter without Isolation is immediately reacted with a compound of the formula (III) and the compounds of the formula (I) according to the invention are thus obtained 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 a two-phase system, such as aqueous sodium or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer catalyst, such as, for example, 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 then the water is separated off in the customary manner.

Für die erfindungsgemäßen 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. I:n 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). I: n generally 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 0,01-01 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, 1 mol of the compounds of the formulas (Va), (Vb), (Vc) or (VI) is preferably employed in 2 mol of hydrogen and 0.01-01 mol of catalyst a. 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 (I) 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 (I) 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. The case may arise that certain isomers have a greater activity than others, so that it may be expedient to prepare or isolate the more active components. All isomers are claimed according to the invention.

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

  • 2-Benzyloxymethyl-5-methyl-tetrahydrofuran
  • 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-terahydrofuran
  • 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-athyl-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-tertahydrofuran
  • 2-Benzyloxymethyl-2-propyl-tetrahydrofuran
  • 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-tertahydrofuran
  • 2-Benzyloxymethyl-2,5,5-trimethyl-tertahydrofuran
  • 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-tertahydro- furan
  • 2-Benzyloxymethyl-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 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-tetrahydrofaran
  • 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-tetrahydrofuran
  • 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-lenzyloxymethyl-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-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-äthyl-tetrahydrofuran
  • 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
  • 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
  • 2-(2-Chlorbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(2-Brombenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(2-Methylbenzyloxymethyl)-5-methoxymethyl-tetrahydrofuran
  • 2-(4-Fluorbenzyloxymethyl)-5-methoxymethyl-tetrah:7drofuran
  • 2-(2,6-Dichlorbenzyloxymethyl)-5-methcxymethyl-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-tetrahydrofuran
  • 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-methylterahydrofuran
  • 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-tertahydrofuran
  • 2-benzyloxymethyl-2-propyl-tetrahydrofuran
  • 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-propyltertahydrofuran
  • 2-benzyloxymethyl-2,5,5-trimethyl-tertahydrofuran
  • 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-tertahydrofuran
  • 2-benzyloxymethyl-2-propyl-5,5-dimethyl-tetrahydrofuran
  • 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-tetrahydrofaran
  • 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-tetrahydrofuran
  • 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-lenzyloxymethyl-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-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-ethyl-tetrahydrofuran
  • 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
  • 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
  • 2- (2-chlorobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (2-bromobenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (2-methylbenzyloxymethyl) -5-methoxymethyl-tetrahydrofuran
  • 2- (4-fluorobenzyloxymethyl) -5-methoxymethyl-tetrah: 7 drofuran
  • 2- (2,6-dichlorobenzyloxymethyl) -5-methcxymethyl-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 understood to mean 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 (Sinapis), 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).
The active compounds according to the invention can be used, for example, in the following plants:
  • Dicotyledon weeds of the genera: mustard (Sinapis), 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 Burlap (Xanthium), Winch (Convolvulus), Morning Glory (Ipomoea), Knotweed (Polygonum), Sesbanie (Sesbania), Ambrosia (Ambrosia), Scratch Thistle (Cirsium) Thistle (Carduus), Goose Thistle (Sonchus), Nightshade (Solanum), Marsh Cress (Rorippa), Rotala, Ciderweed (Lindernia), Deadnettle (Lamium), Honorary Award (Veronica), Schönmalve (Abutilon), Emex, Stecheapfel (Datura), Violet (Viola), hemp nettle, hollow tooth (galeopsis), poppy (papaver), knapweed (centaurea).

Dicotyle Kulturen der Gattungen: Baumwolle (Gossypium), Sojabohne (Glycine), Rübe (Beta), Möhre (Daucus), Gartenbohne (Phaseolus), Erbse (Pisum), Kartoffel (Solanum), Lein (Linum), Prunkwinde (Ipomoea), Bohne (Vicia), Tabak (Nicot:.ana), Tomate (Lycopersicon), Erdnuß (Arachis), Kohl (Brassica), Lattich (Lactuca), Gurke (Cucumis), Kürbis (Cuburbita).Dicotyle cultures of the genera: Cotton (Gossypium), soybean (Glycine), turnip (Beta), carrot (Daucus), haricot bean (Phaseolus), pea (Pisum), potato (Solanum), flax (Linum), morning glory (Ipomoea), Bean (Vicia), tobacco (Nicot: .ana), tomato (Lycopersicon), peanut (Arachis), cabbage (Brassica), cos (Lactuca), cucumber (Cucumis), pumpkin (Cuburbita).

Monokotyle Unkräuter der Gattungen: HUhnerhirse (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).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 (Lolium), Trespe (Bromus), Oat (Avena), Cypergrass (Cyperus), Black Millet (Sorghum), Quecke (Agropyron), Dog's Toothgrass (Cynodon), Monocharia, Fimbristylis, Arrow Herb (Sagittaria), Sumpfried (Sagittaria) Eleocharis), ledges (Scirpus), Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, ostrich grass (Agrostis), foxtail grass (Alopecurus), wind straw (Apera).

Monokotyle Kulturen der Gattungen: Reis (Oryza), Mais (Zea), Weizen (Triticum), Gerste (Hordeum), Hafer (Avena), Roggen (Secale), Mohrenhirse (Sorghum), Hirse (Panicum), Zuckerrohr (Saccharum), Ananas (Ananas), Spargel (Asparagus), Lauch (Allium).Monocot crops of the genera: Rice (Oryza), 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 Unkrautbe- . kämpfung 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 wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weeding. fighting 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 verflüssigten 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 syn-' thetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester,Polyoxy- äthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglycol-Äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin- Sulfitablauge:a 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 manufactured in a known manner, e.g. B. 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. In the case of the use of water as an extender, e.g. B. organic solvents can 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, e.g. B. 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 those liquids which are gaseous at normal temperature and pressure, e.g. B. 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; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. Lignin sulfite waste liquor: a and methyl cellulose.

Die crfindungsgemäßen 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 Fertiqformulierung 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 formulation or tank mix being possible.

Besonders hervorzuheben sind die Kombinationen der.erfindungsgemäßen Wirkstoffe mit 4-Amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-on (Metamitron) für Rübenkulturen, 4-Amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5(4H)-on (Metribuzin) für Sojabohnen, Tomaten und Kartoffeln und 2-Chlor-4-äthylamino-6-isopropylamino-1,3,5-triazin (Atrazin) für Mais und Sojabohnen, mit 3-(3,4-Dichlorphenyl)-1,1-dimethylharnstoff (Diuron) und 3-(3-Trifluormethylphenyl)-1,1-dimethylhamstoff (Fluomethuron) für Baumwolle.Of particular note are the combinations of the active compounds according to the invention with 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (metamitron) for beet crops, 4-amino-6-tert. -butyl-3-methylthio-1,2,4-triazine-5 (4H) -one (metribuzin) for soybeans, tomatoes and potatoes and 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (Atrazine) for corn and soybeans, with 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diuron) and 3- (3-trifluoromethylphenyl) -1,1-dimethylurea (fluomethuron) for cotton.

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 Pflenzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden. Die aufgewandte Wirkstoffmenge kann in größeren Bereichen schwanken. Sie hängt im wesentlichen von der Art des gewünschtem 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 active compounds according to the invention can be applied both after and in particular before emergence of the plants. 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.

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 destruction

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

Figure imgb0017
HerstellungsbeispieleActive ingredients, application rates and results are shown in the table below:
Figure imgb0017
 Manufacturing examples

Beispiel 1example 1

Figure imgb0018
Figure imgb0018

(Verfahrensvariante 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-Fluorbenzyloxymethyl)-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 TabeIle 1 aufgeführten Verbindungen hergestellt werden.

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

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:

  • 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-Hyroxy- propyl)-furan zugetropft.
  • 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.
  • 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.
(a) The 2- [1- (2-chlorobenzyloxy) propyl] furan used as the starting product according to Example 2 can be prepared as follows:
  • 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- Hyroxypropyl) furan added dropwise.
  • 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.
  • 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.

Claims (6)

1.) Tetrahydrofuran-Derivate der Formel
Figure imgb0025
in welcher R1 bis R6 gleich oder verschieden sind und für Wasserstoff, Alkyl, Halogenalkyl, Alkoxyalkyl, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyloxyalkyl stehen, R5 und R6 auch gemeinsam für einen gesättigten carbbcyclischen Ring stehen, R1 für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkoxyalkyl, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyloxyalkyl steht, R8 und R9 gleich oder verschieden sind und für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkoxy, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Benzyl und Benzyloxy stehen, R10 für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Halogenalkyl oder gegebenenfalls substituiertes Phenyl steht und Y für gegebenenfalls substituiertes Aryl steht, mit der Maßgabe, daß, falls Y für Phenyl steht, dieses substituiert sein muß, wenn R' bis R'0 Wasserstoff bedeuten. 1.) Tetrahydrofuran derivatives of the formula
Figure imgb0025
 in which R 1 to R 6 are identical or different and represent hydrogen, alkyl, haloalkyl, alkoxyalkyl, optionally substituted phenyl or optionally substituted benzyloxyalkyl, R 5 and R 6 also together represent a saturated carbbcyclic ring, R 1 represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, optionally substituted phenyl or optionally substituted benzyloxyalkyl, R 8 and R 9 are identical or different and represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, optionally substituted phenyl or optionally substituted benzyl and benzyloxy, R 10 represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl or optionally substituted phenyl and Y represents optionally substituted aryl, with the proviso that if Y represents phenyl, this must be substituted if R 'to R' 0 are hydrogen. 2.) Verfahren zur Herstellung von Tetrahydrofuran-Derivaten, dadurch gekennzeichnet, daß man (a) Alkoholate von 2-Hydroxymethyl-tetrahydrofuran-Derivaten der Formel
Figure imgb0026
in welcher R' bis R9 die oben angegebene Bedeutung haben und M für ein Alkali- oder Erdalkalimetall steht, mit einer Verbindung der Formel
Figure imgb0027
in welcher R10 und Y die oben angegebene Bedeutung haben und Z für Halogen, insbesondere Chlor oder Brom, den Mesylat- oder Tosylat-Rest steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder daß man (b) Diole der Formel
Figure imgb0028
in welcher R1 bis R10 und Y die oben angegebene Bedeutung haben, in Gegenwart eines sauren Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels erhitzt; oder daß man (c) diejenigen Verbindungen der Formel (I), in denen entweder R1 und R7 oder R1 und R4 oder R4 und R5 für Wasserstoff stehen, dadurch erhält, daß man Dihydrofuran-Derivate der Formeln
Figure imgb0029
Figure imgb0030
 und/oder
Figure imgb0031
in welchen R1 bis R10 und Y die oben angegebene Bedeutung haben, in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert; oder daß man (d) diejenigen Verbindungen der Formel (I), in denen R1, R 4, R 5 und R 7 für Wasserstoff stehen, dadurch erhält, daß man Furan-Derivate der Formel
Figure imgb0032
in welcher R2, R3, R6, R8, R9, R10 und Y die oben angegebene Bedeutung haben, in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels mit Wasserstoff hydriert. 2.) Process for the preparation of tetrahydrofuran derivatives, characterized in that ( a ) Alcoholates of 2-hydroxymethyl-tetrahydrofuran derivatives of the formula
Figure imgb0026
 in which R 'to R 9 have the meaning given above and M represents an alkali or alkaline earth metal, with a compound of the formula
Figure imgb0027
 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, if appropriate in the presence of a diluent, or that (b) Diols of the formula
Figure imgb0028
 in which R 1 to R 10 and Y have the meaning given above, heated in the presence of an acid catalyst and optionally in the presence of a diluent; or that one (c) those 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, obtained by dihydrofuran derivatives of the formulas
Figure imgb0029
Figure imgb0030
 and or
Figure imgb0031
 in which R 1 to R 10 and Y have the meaning given above, hydrogenated in the presence of a catalyst and optionally in the presence of a diluent with hydrogen; or that one (d) those compounds of the formula (I) in which R 1 , R 4 , R 5 and R 7 are hydrogen are obtained by reacting furan derivatives of the formula
Figure imgb0032
 in which R2, R 3 , R6, R 8 , R9, R 10 and Y have the meaning given above, hydrogenated in the presence of a catalyst and optionally in the presence of a diluent with hydrogen. 3.)Herbizide Mittel, gekennzeichnet durch einen Gehalt an Tetrahydrofuran-Derivaten gemäß Anspruch 1.3.) Herbicidal agents, characterized by a content of tetrahydrofuran derivatives according to claim 1. 4.)Verfahren zur Bekämpfung von unerwünschtem Pflanzenwachstum, dadurch gekennzeichnet, daß man Tetrahydrofuran-Derivate gemäß Anspruch 1 auf die unerwünschten Pflanzen oder ihren Lebensraum einwirken läßt.4.) Process for combating undesirable plant growth, characterized in that tetrahydrofuran derivatives according to claim 1 are allowed to act on the undesired plants or their habitat. 5.)Verwendung von Tetrahydrofuran-Derivaten gemäß Anspruch 1 zur Bekämpfung von unerwünschtem Pflanzenwachstum.5.) Use of tetrahydrofuran derivatives according to claim 1 for combating undesirable plant growth. 6.)Verfahren zur Herstellung von herbiziden Mitteln, dadurch gekennzeichnet, daß man Tetrahydrofuran-Derivate gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt.6.) Process for the preparation of herbicidal compositions, characterized in that tetrahydrofuran 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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EP0013581A1 (en) * 1979-01-08 1980-07-23 Shell Internationale Researchmaatschappij B.V. Tetrahydrofuran derivatives, a process for their preparation, herbicidal compositions containing them and a method of controlling undesired plant growth using them
DE3101461A1 (en) * 1980-01-21 1982-01-07 Shell Internationale Research Maatschappij B.V., 2596 's-Gravenhage Unsaturated alcohols and their use for the preparation of oxolanes
EP0064306A1 (en) * 1981-05-01 1982-11-10 Shell Internationale Researchmaatschappij B.V. Substituted tetrahydrofuran herbicides
US4400198A (en) * 1980-01-21 1983-08-23 Shell Oil Company Herbicidal tetrahydrofuran derivatives
EP0081893A3 (en) * 1981-12-16 1984-02-08 Shell Internationale Research Maatschappij B.V. Oxabicycloalkane herbicides
US4439225A (en) * 1982-06-14 1984-03-27 Shell Oil Company Herbicidal cyano-tetrahydrofuranylmethyl ether and cyano-tetrahydropyranylmethyl ether derivatives
US4493936A (en) * 1982-06-14 1985-01-15 Shell Oil Company 2-Cyano-tetrahydrofuran-5-methanols
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
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
EP0183650A1 (en) * 1984-11-27 1986-06-04 Ciba-Geigy Ag Phenyl hydrazines, process for their production and their use in pest control
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
AT387931B (en) * 1987-08-13 1989-04-10 Iag Ind Automatisierungsges M Hot press for producing disc-brake pads
AT390413B (en) * 1988-07-20 1990-05-10 Steinbach Gerhard Ludwig Self-adhesive film for motor-vehicle bodies
AT392238B (en) * 1987-04-16 1991-02-25 Jenbacher Werke Ag Device for controlling compressed-air-controlled brakes on rail vehicles
AT392965B (en) * 1986-10-15 1991-07-25 Erba Farmitalia METHOD FOR THE PRODUCTION OF AZETIDINONES
AT394978B (en) * 1986-08-20 1992-08-10 Erlau Ag Eisen Drahtwerk TIRE CHAIN
AT396897B (en) * 1990-12-21 1993-12-27 Haltmeier Georg Agent for impregnating wood
AT397333B (en) * 1988-06-20 1994-03-25 Elin Union Ag Device for fixing components
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
AT399074B (en) * 1991-12-23 1995-03-27 Lenhard Ges M B H DEVICE FOR HOLDING BOARD
AT399414B (en) * 1989-03-21 1995-05-26 Rudolf Dipl Ing Winkler Distance measuring device for motor vehicles
EP1621111A1 (en) * 2004-07-28 2006-02-01 Compin Sitz für öffentliche Verkehrsmittel
WO2016053320A1 (en) 2014-09-30 2016-04-07 Hewlett-Packard Development Company, L.P. Gesture based manipulation of three-dimensional images
EP2420223B1 (en) 2008-03-17 2017-07-19 Novartis Ag Aqueous pharmaceutical compositions containing borate-polyol complexes
US11032035B2 (en) 2000-09-13 2021-06-08 Qualcomm Incorporated Signaling method in an OFDM multiple access system
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013581A1 (en) * 1979-01-08 1980-07-23 Shell Internationale Researchmaatschappij B.V. Tetrahydrofuran derivatives, a process for their preparation, herbicidal compositions containing them and a method of controlling undesired plant growth using them
DE3101461A1 (en) * 1980-01-21 1982-01-07 Shell Internationale Research Maatschappij B.V., 2596 's-Gravenhage Unsaturated alcohols and their use for the preparation of oxolanes
US4400198A (en) * 1980-01-21 1983-08-23 Shell Oil Company Herbicidal tetrahydrofuran derivatives
EP0064306A1 (en) * 1981-05-01 1982-11-10 Shell Internationale Researchmaatschappij B.V. Substituted tetrahydrofuran herbicides
EP0081893A3 (en) * 1981-12-16 1984-02-08 Shell Internationale Research Maatschappij B.V. Oxabicycloalkane herbicides
US4439225A (en) * 1982-06-14 1984-03-27 Shell Oil Company Herbicidal cyano-tetrahydrofuranylmethyl ether and cyano-tetrahydropyranylmethyl ether derivatives
US4493936A (en) * 1982-06-14 1985-01-15 Shell Oil Company 2-Cyano-tetrahydrofuran-5-methanols
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
EP0183650A1 (en) * 1984-11-27 1986-06-04 Ciba-Geigy Ag Phenyl hydrazines, process for their production and their use in pest control
AT394978B (en) * 1986-08-20 1992-08-10 Erlau Ag Eisen Drahtwerk TIRE CHAIN
AT392965B (en) * 1986-10-15 1991-07-25 Erba Farmitalia METHOD FOR THE PRODUCTION 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
US11032035B2 (en) 2000-09-13 2021-06-08 Qualcomm Incorporated Signaling method in an OFDM multiple access system
EP1621111A1 (en) * 2004-07-28 2006-02-01 Compin Sitz für öffentliche Verkehrsmittel
EP2420223B1 (en) 2008-03-17 2017-07-19 Novartis Ag Aqueous pharmaceutical compositions containing borate-polyol complexes
WO2016053320A1 (en) 2014-09-30 2016-04-07 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

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