Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/42—Singly bound oxygen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/12—Radicals substituted by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
  • F01D1/00—Non-positive-displacement machines or engines, e.g. steam turbines

Definitions

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

Landscapes

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

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Publications (2)

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Citations (1)

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• 1977
  • 1977-06-01 DE DE19772724675 patent/DE2724675A1/de not_active Withdrawn
• 1978
  • 1978-05-22 DD DD78205504A patent/DD137320A5/xx unknown
  • 1978-05-29 PT PT68098A patent/PT68098A/pt unknown
  • 1978-05-29 IL IL54802A patent/IL54802A0/xx unknown
  • 1978-05-30 IT IT7823999A patent/IT7823999A0/it unknown
  • 1978-05-30 ZA ZA00783090A patent/ZA783090B/xx unknown
  • 1978-05-30 JP JP6394878A patent/JPS543057A/ja active Pending
  • 1978-05-31 BR BR787803476A patent/BR7803476A/pt unknown
  • 1978-05-31 DK DK242578A patent/DK242578A/da unknown
  • 1978-06-01 DE DE7878100007T patent/DE2860975D1/de not_active Expired
  • 1978-06-01 EP EP78100007A patent/EP0000002B1/de not_active Expired

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