Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
• • 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<
  • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C275/30—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups

Definitions

• the present invention relates to a new substituted phenylurea, to its preparation, to the herbicidal compositions containing it and to a process for selective weeding of certain crops using these compositions.
• a subject of the invention is also trifluoromethyl-3-ethyl-4-aniline, its preparation and its use as an intermediate for the manufacture of chemical compounds. It is well known that certain tri-substituted phenylureas have interesting selective herbicide properties.
• Belgian patent 594.227 describes herbicidal agents containing, as active material, N-tri-fluoromethyl-3 phenyl N'N-dimethylurea usable as total or selective weedkiller after 2.5 kg / ha of corn. Since then, this compound has been used commercially only on cotton, the margin of selectivity for other crops being considered too narrow.
• 4-alkylphenyl N'N'-dimethy.lureas are known, having good selective herbicide properties on crops, especially on cereals.
• their selectivity on cotton has never been used, the results of outdoor experiments have not confirmed those of greenhouse tests.
• N-trifluoromethyl-3-ethyl-4-phenyl N'N 'dimethylurea instead of accumulating the reduced selectivities on cereals, corn and cotton that could be expected from the simultaneous presence of the trifluoromethyl subtuants in position 3 and lower alkyl in position 4 on the phenyl nucleus, presents a cumulative desmeileufes selectivities, these being further improved compared to the aforementioned ureas.
• French patent 2,001,791 describes a family of substituted phenylureas whose substituents cover those of the compounds according to the invention, but this family includes a considerable number of possible compounds (more than 100,000) and the only subfamily actually illustrated by physico-chemical characteristics does not apply to products comprising a trifluoromethyl group on the phenyl ring.
• the selectivity of certain compounds, including in particular chltoluron, is illustrated on cereals, their behavior on cotton is not the subject of any test result or even mentioned in the description of the patent cited.
• the present invention therefore relates to a new chemical compound of formula:
• the compounds according to the invention can be prepared according to methods known per se. First of all, the trifluoromethyl-4-ethyl-phenyl isocyanate can be condensed on the dimethylamine according to the scheme:
• This reaction is carried out in an organic solvent medium inert under the conditions of the reaction, for example an aromatic solvent such as toluene or chlorobenzene, at room temperature, preferably with stirring.
• an aromatic solvent such as toluene or chlorobenzene
• the isocyanate used can be obtained in a manner known per se by reacting 'phosgene on trifluo rométhyl 3-ethyl-aniline 4, the reagents being added as a solution in an inert organic solvent, for exeple an inert aromatic solvent , under the reaction conditions such as toluene or chlorobenzene, at a temperature between 0 ° (: and the boiling point of the solva A relatively high temperature promotes the release of hydrochloric acid from the reaction:
• Another mode of preparation consists in reacting hexametapil and carbon dioxide on 3-trifluoromethyl-4-ethyl aniline according to the scheme:
• the compound according to the invention can be prepared by the action of dimethylcarbamyl chloride on trifluoromethy-3 ethyl-4 aniline according to the scheme:
• Trifluoromethy1-3 ethyl-4 aniline a liquid product which distills at 96-97 ° C under 16 mm Hg, is a new synthesis intermediate which can be prepared by catalytic hydrogenation d ⁇ . corresponding nitrous derivative in the presence, for example, of palladium on activated carbon, in methanolic medium according to the scheme:
• the nitro derivative can be prepared by nitration using a sulfonitric mixture of orthotrifluoromethyl ethylbenzene according to the scheme:
• the orthotirifluoromethy1 ethylbenzene can be obtained by catalytic hydrogenation, in the presence of palladium on activated carbon, in an alkaline methanolic medium, of 1 'orthotrifluoromethy1 trichloro-2' 2 '2' ethylbenzene according to the scheme:
• the trichloride derivative can be obtained by reaction, in acetone, in the presence of cupric chloride of dichloro vinylidene on a halide, in particular the diazonium chloride of the trifluoromethy 1-2 aniline according to the
• the product obtained (with a yield of 63%) melts at 105-106 ° C.
• the reaction is carried out with stirring and at a temperature in the region of 0 ° C. After the end of the flow of the aniline solution, the medium is allowed to return to room temperature, then slowly heated until boiling. After the gas evolution of the hydrochloric acid formed and the excess of phosgene has ended, the reflux is maintained for another 1 hour. The toluene is then evaporated and a liquid, with a boiling point of 50-51 ° C under 1 mm of mercury, is obtained with a yield of 95%.
• Example 2 Preparation of the compound according to the invention, according to the second process.
• a three-necked flask provided with a condenser and a carbon dioxide inlet tube plunging near the bottom of the flask and with stirring, 8.1 g (0.0427 mol) of trifluoromethyl 1-3 ethyl are introduced.
• 4 aniline, 7.0 g (0.0427 mole) of hexametapil and 22 ml of previously dried pyridine The temperature is adjusted to 60 ° C. and the carbon dioxide stream is passed through for 6 hours. After dry evaporation and taken up in 20% ethanol, the urea precipitates.
• Hydrogen is introduced under a pressure of 10 bars into a mixture heated to 48-50 ° C,
• Trifluoromethyl-2 nitro-4 ethylbenzene is obtained according to the following process:
• Trifluoromethyl 1-2 ethylbenzene is prepared as follows: The following are introduced into a 1000 ml autoclave
• the organic phase is decanted and the aqueous phase treated with methylene chloride.
• the organic phase and the chloromethylenic extracts are combined, washed with water and dried over anhydrous sodium sulfate. After evaporation of the methylene chloride, a liquid product is obtained, which distills at 40-41 ° C under 15 mm of mercury, the overall yield being 91%.
• Trifluoromethyl-2 (trichloro-2'2'2 ethyl-) benzene is obtained as follows: the diazonium salt is first prepared by diazotization of trifluoromethyl 1-2 aniline. A solution of 69 g (l mole) of sodium nitrite in 150 ml of water is poured simultaneously onto 130 ml of 10 N hydrochloric acid, as well as the solution into 500 ml of 1-97 water, 5 g (1 mole) trifluoromethyl 1-2 aniline hydrochloride. After reaction at a temperature of between 0 and 5 ° C., a clear light yellow solution of trifluoromethyl 1-2 benzene diazonium chloride is obtained.
• This solution is poured onto a mixture of 116.4 g (1.2 mole) of dichlorovinylidene, one liter of acetone and 10 g of copper chloride dihydrate dissolved in 50 ml of water.
• the reaction is maintained at a temperature of 27-28 ° C.
• the dichloro-vinylidene entrained by the evolution of nitrogen is condensed in the cooler cooled to -10 ° C by a circulation of brine.
• stirring is continued and heating at 30 ° C. until the end of the evolution of nitrogen.
• the reaction mixture is then diluted in 5 liters of water.
• Example 4 Pre-emergent and post-emergent herbicidal activity of crops and weeds.
• the pots are treated by spraying a quantity of porridge per pot corresponding to a volume of 500 l / ha and containing the active material at the dose considered.
• the slurry is prepared by diluting with water an emulsifiable concentrate having the following composition by weight: active material to be tested 20% emulsifying agent: nonylphenol oxyethylenated with 17 ethylene oxide 10% solvent (xylene) 70% at the desired dilution, containing the active ingredient at the dose considered.
• active material to be tested 20% emulsifying agent: nonylphenol oxyethylenated with 17 ethylene oxide 10% solvent (xylene) 70% at the desired dilution, containing the active ingredient at the dose considered.
• the tests were carried out for doses of active material ranging from 0.25 kg / ha to 8 kg / ha.
• the treated pots are then placed in tubs intended to receive the irrigation water, under subirrigation, and kept for 35 days at room temperature under 70% relative humidity.
• the destruction rate is compared to a control treated under the same conditions with a spray dispersion not containing the active ingredient.
• Crops both crops and weeds tested, were as follows: Crops:
• Vulpin (Alopecurus myosuro ⁇ des) VU
• the compounds tested as active material are:
• both its selectivity threshold will be higher (for example at least equal to 4 kg / ha) and its activity threshold will be lower (for example at most equal to 1 kg / ha), that is to say that the margin between activity and selectivity will be greater, the weedkiller being usable with all the more security for the crop considered.
• Table TIB Activity threshold in kg / ha on post-emergent weeds
• the compound 1 has a herbicidal activity substantially equivalent to that of fluometuron preemergence and incomparably higher postemergence.
• the herbicidal activity of this same compound 1 is obviously much higher than that of compounds A and B both pre- and post-emergence, the latter being inactive at 8 kg / ha except compound B which destroys mustard 8kg / ha postemergence.
• N-trifluoromethy-3 ethyl-4 phenyl N'N'-dimethylurea can therefore be used as active material in the compositions for the selective weeding of crops and in particular of cereals (wheat, barley), corn, cotton and soybeans.
• the dose of active material to be used can vary from 0.25 to 8 kg / ha, in particular according to the type of crop and the nature of the soil. Preferably, this dose is comprised between 0.5 and 5 kg / ha.
• the compound according to the invention is rarely used alone. Most often, it is part of formulations which generally comprise from 0.5 to 95% by weight of the active material according to the invention, a support and / or surfactant (generally from 0 to 10 % by weight, preferably 0.1 to 10%).
• support within the meaning of the present description designates a material, organic or mineral, natural or synthetic, with which the active material is associated to facilitate its application on the plant, on the seeds or on the soil, or its transport or his ma- nipulation.
• the support can be solid (clay, natural or synthetic silicates, resins, waxes, solid fertilizers) or fluid (water, alcohols, ketones, petroleum factions, chlorinated hydrocarbons, liquefied gases).
• the surfactant can be an emulsifying, dispersing or wetting agent, each of which may be ionic or nonionic. Mention may be made, for example, of salts of polyacrylic acids, salts of phenolsulfonic acids or sulphonated naphthalene acids, polycondensates of ethylene oxide on fatty alcohols.
• compositions according to the invention can be prepared in the form of wettable powders, dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspended concentrates and aerosols.
• Wettable powders are usually prepared so that they contain from 20 to 95% by weight of active ingredient and they usually contain, in addition to a solid support, from 0 to 5% by weight of wetting agent, from 3 to 10% by weight of one or more stabilizers and / or other additives, such as penetration agents, adhesives or anti-caking agents, glues, etc.
• a powder wettable - active ingredient (compound N ° l) 50%
• the granules intended to be placed on the ground are usually prepared so that they have dimensions between 0.1 and 2 mm and they can be manufactured by agglomeration or impregnation. In general, the granules contain from 0.5 to 25% of material active and from 0 to 10% by weight of additives such as stabilizers, slow release modifiers, binders and solvents.
• the emulsifiable concentrates applicable in spraying usually contain, in addition to the solvent, and, when necessary, a co-solvent, from 10 to 50% by weight / volume of active material, from 2 to 20% by weight / volume of suitable additives, such as stabilizers, penetrating agents, corrosion inhibitors, and dyes and adhesives.
• a co-solvent from 10 to 50% by weight / volume of active material, from 2 to 20% by weight / volume of suitable additives, such as stabilizers, penetrating agents, corrosion inhibitors, and dyes and adhesives.
• composition of an emulsifiable concentrate the quantities being expressed in g / liter:
• Concentrates in suspension are prepared in such a way as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% by weight of active material, from 0.5 to 15 % by weight of surfactants, from 0.1 to 10% by weight of thixotropic agents, from 0 to 10% by weight of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives, and as a carrier, water or an organic liquid in which the active ingredient is substantially insoluble: certain organic solids or mineral salts can be dissolved in the carrier to prevent sedimentation or as antifreeze for water.
• Aqueous dispersions and emulsions for example, compositions obtained by diluting with of water, a wettable powder or an emulsifiable concentrate according to the invention are included in the general scope of the present invention.
• the emulsions can be of the water-in-oil type or of the oil-in-water type and they can have a thick consistency like that of a "mayonnaise".
• compositions according to the invention may contain other ingredients, for example, protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants as well as other known active materials with pesticidal properties, in particular insecticides or fungicides .

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

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• 1978
  • 1978-07-25 FR FR7822885A patent/FR2435464A1/fr not_active Withdrawn
• 1979
  • 1979-07-09 IL IL57758A patent/IL57758A0/xx unknown
  • 1979-07-13 ES ES482473A patent/ES8202790A1/es not_active Expired
  • 1979-07-20 CS CS795106A patent/CS208667B2/cs unknown
  • 1979-07-23 PT PT69964A patent/PT69964A/pt unknown
  • 1979-07-23 ZA ZA00793754A patent/ZA793754B/xx unknown
  • 1979-07-23 AU AU49132/79A patent/AU4913279A/en not_active Abandoned
  • 1979-07-23 GB GB7925650A patent/GB2027699A/en not_active Withdrawn
  • 1979-07-24 WO PCT/FR1979/000068 patent/WO1980000344A1/fr unknown
  • 1979-07-24 MA MA18734A patent/MA18537A1/fr unknown
  • 1979-07-24 PL PL21732679A patent/PL217326A1/xx unknown
  • 1979-07-24 JP JP50117379A patent/JPS55500454A/ja active Pending
  • 1979-07-24 DD DD79214581A patent/DD145053A5/de unknown
  • 1979-07-25 GR GR59691A patent/GR69974B/el unknown
• 1980
  • 1980-03-11 EP EP79900847A patent/EP0016132A1/de not_active Withdrawn
  • 1980-03-21 DK DK122780A patent/DK122780A/da unknown
  • 1980-03-25 OA OA57062A patent/OA06494A/xx unknown

Non-Patent Citations (1)

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