Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/58—Radicals substituted by nitrogen 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
  • C07C275/48—Y being a hydrogen or a carbon atom
  • C07C275/50—Y being a hydrogen or an acyclic carbon atom

Definitions

• the present invention relates to new ⁇ -substituted pentylurea derivatives, several processes for their preparation and their use as fungicides.
• the fungicidal activity of some isonitrosocyanacetamide derivatives is also known (cf. DT-OSS 1 693 052, 2 118 317, 2 312 956, 2 350 910, 2 436 654, 2 436 655, 2 603 643 and 2 635 697 and US-PSS 3,625,987, 3,769,423, 3,919,284, 3,954,992 u: id 3,957,847.
• the effectiveness is not reliable at low application rates. and plant damage is seen at normal concentrations.
• the substances according to the invention can exist as oxime derivatives in two different geometric structures:
• the spatial structure is omitted;
• the given formulas (Ia) should in any case also include the corresponding formula according to the spatial structure (Ib).
• the compounds according to the invention show a good fungicidal action. They are protective, curative and even eradicative, they also have systemic and / or locosystemic properties. Surprisingly, they show better plant tolerance than the isonitrosocyanacetamide derivatives known from the prior art. Compared to the dithiocarbamidates and the N-trichloromethylthio-tetrahydrophthalimide, they have the advantage of curative and eradicative effects.
• the compounds according to the invention represent a valuable enrichment of the technology because of the many possibilities of their superior biological application.
• Another essential aspect of this invention is that new active ingredients with properties that are useful in practice are made available at a time because of signs of resistance of older active ingredients there is a pronounced need for new fungicides.
• R preferably represents R 1
• R preferably represents alkyl having 1 to 6 carbon atoms; furthermore for such alkyl having 1 to 2 carbon atoms, which is represented by a vinyl group, by an alkylcarbonyl group having 2 to 5 carbon atoms, by alkoxycarbonyl having 2 to 5 carbon atoms, by aminocarbonyl, by N-alkylaminocarbonyl or N-cycloalkylaminocarbonyl up to 7 carbon atoms, is substituted by N-phenylaminocarbonyl, which may contain lower alkyl substituents and / or chlorine atoms in the phenyl radical, or for benzyl, which contains methyl, methoxy, methylenedioxy, nitro or trifluoromethyl groups or Can carry 1 to 2 chlorine atoms as substituents.
• R is particularly preferred for the following structural elements of R 1 : methyl, ethyl, methoxycarbonylmethyl, 1- (methoxycarbonyl) ethyl-1, tert-butylcarbonylmethyl and aminocarbonylmethyl.
• the 1- (5-substituted pentyl) -3- (2-cyano-2-oximinoacetyl) ureas of the formula IV required as starting materials according to process variants b) to c) have hitherto not been known. They are prepared by using, for example, W-cyanopentyl isocyanate (cf. Liebigs Ann. Chem. 562, 104 (1949), cyanopentyl carbamic acid chloride (DT-OS 2 626 828 rLe A 17 135]), ⁇ -isocyanato-caproic acid alkyl ester (cf. DT- OS 1 913 273), ⁇ -dhenoxycarbonylamino-caproic acid (cf.
• DT-OS 1 720 606 also Chem. Abstr. 71, 50689 (1969)
• ⁇ -isocyanatocaproic acid chloride DT-AS 1 222 919
• ⁇ -phenoxycarbonylamino-caproic acid is used as the starting material
• 5-carboxypentylurea is obtained as the ammonium salt. Acidification with a mineral acid gives the free ureidopentylcarboxylic acid.
• said urea is dissolved in water or in mixtures of water with methanol, ethanol, propanol, glycol monomethyl ether, glycol monoethyl ether, acetonitrile, dioxane or tetrahydrofuran with a salt of nitrous acid at a temperature of 20 to 70 ° C., preferably at 40 to 50 ° C, by adding an organic carboxylic acid, such as acetic acid or a mineral acid, such as sulfuric acid or by mixing organic carboxylic acids with mineral acids to a pH of 4 to 6, preferably to a pH of 5 to 5.6 brought.
• the oximation is complete after about 2 hours.
• the reaction mixture is brought to a pH of 1.8 to 3.5, preferably of, by adding further mineral acid at a temperature which is between the freezing point of the solution and about 30 ° C., preferably between +2 and 10 ° C. about 2.
• the 1- (5-substituted pentyl) -3- (2-cyan-2-oximino-acetyl) urea of the formula IV is either separated by diluting the reaction mixture with water and, after the product has been separated off, washed with water and dried, or the compound is taken up in a solvent such as ethyl acetate, methyl acetate, ethyl formate or methyl propionate, the solution of the reaction product obtained is washed with water, dried with sodium sulfate, for example, and product IV is precipitated by adding petroleum ether, or the solution is evaporated.
• urea of the formula IV can also be reacted with an ester of nitrous acid, e.g. Isoamyl nitrite, on a 1- (5-substituted pentyl) -3- (2-cyanoacetyl) urea can be obtained.
• an ester of nitrous acid e.g. Isoamyl nitrite
• the isocyanates of the formula VII or the carbamic acid halides of the formula VIII required for the reaction according to process d) are likewise known compounds; the carbamic acid halides are prepared by addition of hydrogen halide to the isocyanates of the formula VI.
• the carbonic acid esters required by process e) are also known compounds. Worth mentioning are: dimethyl pyrocarbonate, diethyl pyrocarbonate, ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, sec-butyl chloroformate, isobutyl chloroformate, allyl chloroformate and methyl chloroformate.
• the 2-cyano-2-alkoximinoacetamide is dissolved in an inert water-free solvent such as dioxane, tetrahydrofuran or diisopropyl ether with e.g. Sodium hydride or potassium tert-butoxide was converted into the anion of the amide and then reacted with ⁇ -substituted pentyl isocyanate at a moderately elevated temperature.
• the reaction product according to the invention is precipitated by adding water or the solution of the reaction product in the organic solvent is washed out and carefully evaporated.
• reaction is preferably carried out in the presence of polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, toluene, dioxane, Tetrahydrofuran, acetonitrile, benzonitrile or ethyl acetate.
• polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, toluene, dioxane, Tetrahydrofuran, acetonitrile, benzonitrile or ethyl acetate.
• All customary hydrogen halide acceptors can be used as acid binders in process b). These include alkali hydroxides, alkali carbonates and other suitable alkali salts. Examples include Sodium carbonate, sodium bicarbonate, borax (disodium tetraborate) and trilithium phosphate. If you work in the presence of water, it can be neutralized by adding sodium hydroxide solution.
• Organic acid binders can also be used, e.g. tertiary amines. These include triethylamine, dimethylbenzylamine, dimethylaniline, pyridine, picoline, quinoline, ethyldiisopropylamine and ethyldicyclohexylamine.
• reaction temperatures can be varied within a wide range in process b). Generally one works between about -50 and about + 120 ° C, preferably between -5 and + 80 ° C.
• the reactions can also be carried out in mixtures of water and a water-miscible organic solvent or in heterogeneous systems consisting of water and a water-immiscible or only partially miscible solvent; the temperature range of the reaction here lies between the freezing point of the water or the solidification point of the aqueous solution and approximately 100 ° C., preferably -5 ° to + 80 ° C.
• the reaction must be carried out at low temperatures, preferably at -30 ° C. to -10 ° C., and weakly acidified after the reaction has ended.
• Reaction temperatures and reaction time in process b) are determined by the activity of the starting products of the formula V.
• a small amount of an iodide is added to the mixtures before the reaction, unless a compound of the formula V with iodine is used as the leaving group.
• the reaction rate is increased and the risk of the formation of compounds with a nitron structure is reduced (cf. Houben-Weyl, "Methods of Organic Chemistry", Volume 10/4, Stuttgart (1968)).
• Process d) according to the invention is expediently carried out in a diluent.
• All inert organic solvents are suitable as such.
• Dimethyl sulfoxide, dimethylformamide, dimethylacetamide and ethyl acetate are preferably used, and also ketones, such as e.g. Acetone, methyl ethyl ketone and diethyl ketone, also ether, such as e.g. Tetrahydrofuran, chlorinated hydrocarbons, e.g. Methylene chloride and chloroform, nitriles such as e.g. Acetonitrile and benzonitrile and aromatics such as e.g. Toluene and chlorobenzene.
• ketones such as e.g. Acetone, methyl ethyl ketone and diethyl ketone
• ether such as e.g. Tetrahydrofuran
• chlorinated hydrocarbons e.g. Methylene chlor
• Basic catalysts can be used as auxiliaries in process d); for example tertiary amines, such as triethylamine or pyridine, and tin-2-ethylhexanoate.
• tertiary amines such as triethylamine or pyridine
• tin-2-ethylhexanoate instead of the isocyanates of the formula VII, the corresponding carbamic acid halides of the formula VIII can be used in each case Find. In this case, additional tertiary amine is required to bind the hydrohalic acid released in the reaction.
• reaction temperatures can be varied within a wide range in process d). Generally one works in the range between -20 and + 120 ° C, preferably between +10 and 70 ° C.
• the active compounds according to the invention precipitate in crystalline form or remain dissolved in the organic solvent and can then be separated out after washing out the solution with water by carefully concentrating the solution or by adding a few clear organic solvents, such as carbon tetrachloride, cyclohexane or dibutyl ether.
• the compounds according to the invention are dissolved in a water-miscible solvent, they can also be filled in by adding water. As far as the special conditions of the work-up processes allow, the solutions of the active substances according to the invention or the still solvent-moist suspensions of the active substances should be made weakly acidic.
• the compounds according to the invention partly decompose at a higher temperature; in these cases the melting points can only be determined with little accuracy or not at all.
• the presence of certain structural elements can be seen from the NMR spectra.
• the IR spectra also show characteristic absorption bands.
• the active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomyccces, Basidiomycetes, Deuteromycetes.
• the active compounds according to the invention can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They can therefore also be used for soil and seed treatment.
• the active ingredients in particular show a high protective and curative activity against phycomycetes. There are also good effects against Mycosphaerella and Rhizoctonia species and against rust fungi.
• the active compounds according to the invention not only have the good properties of excellent commercial preparations, but also have considerable advantages. These lie primarily in the ability of the substances according to the invention to penetrate the plant. They can be absorbed by the seed surface, by the roots and also by aerial plant organs after external applications. They also have the advantageous ability to have a locosystemic effect, ie to exert a deep effect in the plant tissue and thereby to eliminate fungal pathogens which have already penetrated into the tissue of the host plant.
• some substances according to the invention are also effective as growth regulators for plants.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, P L lver, pastes and granules. These are made in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
• extenders that is liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie 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 carrier materials: natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin, sulfite and methyl cellulose.
• solid carrier materials natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonit
• the substances according to the invention together with sucrose, dextrose, dextrins, with anhydrous calcium sulfate or calcium sulfate hemihydrate, and with carboxylic acids, e.g. Fumaric acid or 4-hydroxylbenzoic acid, or can also be formulated together with weakly acidic ion exchangers.
• carboxylic acids e.g. Fumaric acid or 4-hydroxylbenzoic acid
• the active compounds according to the invention can be present in the formulations in mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
• active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
• the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling. Wet pickling, wet pickling, slurry pickling or incrustation.
• the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.5 and 0.0005 percent by weight, preferably between 0.2 and 0.001.
• amounts of active ingredient of 0.01 to 50 g per kilogram of seed preferably 0.5 to 5 g, are generally required.
• active ingredient For soil treatment, amounts of active ingredient from 1 to 1000 g per cbm of soil, preferably from 10 to 200 g, are required.
• the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
• the spray liquid is used to spray young tomato plants with 2 to 4 leaves until they drip wet.
• the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%.
• the tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans.
• the plants are placed in a humid chamber with 100% humidity and a temperature of 18 to 20 ° C.
• the infestation of the tomato plants is determined after 5 days.
• the rating values received are converted to percent infestation. 0 means no infection, 100% means that the plants are completely infected.
• the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
• Young tomato plants with 2 to 4 leaves are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants stand for 7 hours at 20 ° C and a relative humidity of 100%.
• the plants are sprayed to runoff point with the spray liquid which has been prepared in the above-mentioned manner and then placed in a humid chamber with 100% atmospheric humidity and a temperature of 18 to 20 ° C.
• the infestation of the tomato plants is determined after 5 days.
• the rating values received are converted to percent infestation. 0 t means no infection, 100% means that the plants are completely infected.
• the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to a fine powdery mixture with the desired active ingredient concentration.
• Wheat seed is contaminated with 5 g of Tilletia caries chlamydospores per kg of seed.
• shake the seeds with: the dressing in a sealed glass bottle.
• the seeds are exposed to moist clay under a covering layer of a layer of gauze and 2 cm of moderately moist compost soil in the refrigerator at 10 ° C for 10 days at optimal germination conditions for the spores.
• the germination of the spores on the wheat grains is determined microscopically, each of which contains around 100,000 spores. The fewer spores have sprouted, the more effective the active ingredient will be.
• M an mixes the amount of active ingredient required for the desired active ingredient concentration in the spray liquid with the stated amount of solvent and dilutes the concentrate with the stated amount of water which contains the additives mentioned.
• the spray liquid is used to spray young tomatoes to the point of dripping wet. After drying, the plants are placed in the greenhouse at a temperature of + 20 ° C and approx. 70 relative air humidity.
• the observation period is usually 4 days.
• Preliminary product 550 g (2.47 mol) 1- (5-cyanopentyl) -3- (2-cyanoacetyl) urea, 625 g water, 625 g dioxane, 188 g techn.
• Sodium nitrite is adjusted to a pH value of 5 at 50 ° C. by slowly adding about 15% sulfuric acid. Stir for two hours, then give 5 liters. Water and 5 ltr.
• Ethyl acetate added. It is cooled to 2 ° C. and a pH of 2 is adjusted by further addition of 15% sulfuric acid. The organic phase is separated and the aqueous phase with a second time 2 ltr. Ethyl acetate stirred.
• the ethyl acetate solution is twice with 2 ltr. Water, which contains a small amount of sodium sulfate in solution for better separation, washed and dried twice over sodium sulfate.
• the reaction product is precipitated by adding petroleum ether. It is washed with a mixture of petroleum ether and ethyl acetate in a ratio of 4: 1 and dried at 60 ° C and a pressure of C, 1 mm Hg. Yield: 504 g of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp 147 ° C.
• a second crystal fraction (approx. 70 g) can be obtained from the mother liquor by concentration.
• the product can be recrystallized from water, diethyl ketone or ethyl acetate.
• the compound can also be prepared from 5-aminocapronitrile and potassium cyanate).
• the compound is prepared according to production process b) by methylation of the corresponding hydroxy compound, which is described below. Mp 155 ° C.
• Preliminary product 72 g of 1- (5-aminocarbonylpentyl) -3- (2-cyanoacetyl) urea, 125 ml of water, 125 ml of dioxane, 23.2 g of sodium nitrite and 1 ml of acetic acid are added at 50 ° C. by slowly adding 15% icer sulfuric acid adjusted to pH 4.5 to 5. The mixture is stirred at 50 ° C. for 2 hours, diluted with 600 ml of water and 600 ml of ethyl acetate, then cooled to 20 ° C. and the reaction mixture is adjusted to a pH of 2. The crystals are separated, washed with water and dried in vacuo. 61.3 g of 1- (5-aminocarbonylpentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp 187-189 ° C. are obtained.
• This intermediate is prepared analogously to the intermediate specified in Example 1, starting from 1- (5-aminocarbonylpentyl) urea. Mp 164 v C.
• connection is produced by method b). Mp 172 ° C.
• Preliminary product 48.2 g (0.2 mol) of 1- (5-carboxypentyl) -3- (2-cyanoacetyl) urea, 50 ml of water, 50 ml of dioxane and 15.2 g of sodium nitrite are heated to 50 ° C. It is then added dropwise to a mixture of 13 g of sulfuric acid and 90 g of water to give a pH of 4.6. The mixture is kept at 50 ° C. for a further 2 hours, then cooled to approx. 1 ° C., 400 ml of water are added and the pH is reduced to 2.5 by further dropwise addition of dilute sulfuric acid. The crystals are separated off, washed with water and dried at 60 ° C. in vacuo. The yield is 51.7 g of 1- (5-carboxypentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp. 201 ° C.
• the intermediate product is prepared starting from 1- (5-carboxypentyl) urea in accordance with the information for the intermediate product according to Example 1. Mp 158 ° C.

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• Agronomy & Crop Science (AREA)
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• 1978
  • 1978-05-25 US US05/909,743 patent/US4188401A/en not_active Expired - Lifetime
  • 1978-05-29 PT PT68101A patent/PT68101A/pt unknown
  • 1978-06-01 IL IL7854839A patent/IL54839A0/xx unknown
  • 1978-06-01 DE DE7878100035T patent/DE2860036D1/de not_active Expired
  • 1978-06-01 EP EP78100035A patent/EP0000023B1/fr not_active Expired
  • 1978-06-02 JP JP6587478A patent/JPS543011A/ja active Pending
  • 1978-06-02 IT IT7824170A patent/IT7824170A0/it unknown
  • 1978-06-02 BR BR787803554A patent/BR7803554A/pt unknown
  • 1978-06-02 DD DD78205767A patent/DD137319A5/xx unknown
  • 1978-06-02 DK DK248478A patent/DK248478A/da unknown

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