GB2091248A - Herbicidal propionic acid esters - Google Patents

Herbicidal propionic acid esters Download PDF

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GB2091248A
GB2091248A GB8138135A GB8138135A GB2091248A GB 2091248 A GB2091248 A GB 2091248A GB 8138135 A GB8138135 A GB 8138135A GB 8138135 A GB8138135 A GB 8138135A GB 2091248 A GB2091248 A GB 2091248A
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alpha
signifies
phenoxy
alkyl
trifluoro
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F Hoffmann La Roche AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

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

Description

SPECIFICATION Propionic acid esters The invention is concerned with propionic acid esters of the general formula
wherein R1 signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen, chlorine, bromine or iodine, R3 signifies hydrogen or C1-4-alkyl, R4 signifies hydrogen;C1-4-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which they are attached can also form a C5 8-cycloalkane ring which, if desired, can be substituted with 1 to 3 C1 4-alkyl groups, m, n, and p signify the number 0 or 1 and R5 signifies one of the following groups (a)-(f):: -NHCO-R6 (a) -NH502-R7 (b)
whereby in the above formulae of the groups (a)-(f) R6 signifies hydrogen; C1 6-alkyl; C1 4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and / or nitro, R7 signifies C1 6-alkyl;; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R8 and R9 stand for hydrogen or together signify a bond, trimethylene, tetramethylene, 2butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R11 signifies trifluoromethyl, C1-6-alkoxy, C1 6-alkoxy, C1 6-alkoxy- C1 4-alkyl, C2 7-alkanoyl, C27-alkoxycarbonyl or C2-7-alkoxycarbonyl-C1-4-alkyl, or R10 and R" together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be substituted with 1 to 3 C1 4-alkyl groups and/or 1 C1 4-alkoxy group, whereby, where R10, R11 and the carbon atom form an optionally substituted cyclopentane ring, R' is chlorine, bromine or trifluoromethyl, R12 signifies hydrogen or C1-6-alkyl and R'3 signifies C1 6-alkyl; or phenyl, optionally substituted with halogen, C1 4-alkyl and/or nitro, or R12 and R'3 together with the carbon atom to which they are attached form a C5 7-cycloalkane ring, and R14 and R'5 signify C1 6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 represents a group (d), m, n and p signify the number 0; when R5 represents a group (e), m signifies the number 0 and n and p signify the number 1; and when R5 represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1.
The compounds of formula I possess herbicidal properties and are accordingly suitable as weed control agents and as active substances of weed control compositions. Accordingly, the invention also includes weed control compositions which contain at least one compound of formula I as the active substance, a process for the manufacture of these compounds as well as the use of such compounds or compositions for the control of weeds.
In formula I above the term "halogen" includes fluorine, chlorine, bromine and iodine. The term 'C14-alkyI" or "C16-alkyl" means not only straight-chain but also branched-chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.butyl, n-pentyl, isoamyl, neo-pentyl and n-hexyl.This is also true for groups containing C1 4-alkyl groups or C1 6-alkyl groups such as C14- or C, 6-alkoxy, C2 7-alkoxycarbonyl, C1 4-haloalkyl, C27-alkoxycarbonyl-C14- alkyl, C16-alkoxy-C14-alkyl and C2 7-alkanoyl. When two or more substituents are present in a substituted phenyl group, the substituents can be the same or different. This is also true for the C5 8-cycloalkane ring substituted with alkyl and the cyclopentane ring substituted with alkyl and/or alkoxy. The term "haloalkyl" includes alkyl substituted with one or more halogen atoms.
Since at least one asymmetric carbon atom is present in the molecule, the compounds of formula I can occur in optically active form. As a consequence of the nitrogen-carbon double bond in the compounds of formula I in which R5 signifies a group (d) or a group (e) geometric isomerism also occurs in the case of those compounds in which R10 and R11 or R12 and R'3 have different significances. Such geometric isomers are called the syn- and anti-forms. Independently thereof, an atropic isomerism is also present in certain cases. Formula I is accordingly intended to include the racemates as well as all of these possible isomeric forms.
Independently of one another R1 preferably signifies iodine or trifluoromethyl and R2 preferably signifies hydrogen or chlorine.
When R3 signifies C, 4-alkyl, this is preferably methyl.
R6 preferably signifies C, 6-alkyl.
R7 preferably signifies optionally substituted phenyl.
RS and R9 both preferably signify hydrogen.
The D-forms of the compounds of formula I are especially preferred.
Preferred compounds of formula I are: Succinimidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionate, ethyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]propionoxy]-acetamidate, n-butyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]propionoxy]-acetimidate, 2-isopropylideneaminooxy-ethyl D-2-[p-( -trifluoro-p-tolyloxy)phenoxy]-propionate and diethoxyphosphinylmethyl D-2-[p-(α,α,α;-trifluoro-p-tolyloxy)phenxy]-propionate, The process in accordance with the invention for the manufacture of the compounds of formula I comprises (a) reacting an acid of the formula
wherein R' and R2 have the significance given above, or a reactive derivative thereof, with a compound of the formula
wherein R3, R4, R5, m, n and p have the significance given above and X signifies a leaving group, or (b) reacting a.phenol of the formula
wherein R' and R2 have the significance given above, or an alkali metal salt thereof, with a compound of the formula
wherein R3, R4, R5, m, n and p have the significance given above and Y signifies a leaving group.
Process variant (a) is an esterification which can be carried out according to methods known per se; for example, in accordance with the following variants (a1), (a2) and (a3): Educt (a1) Free acid of formula II, but especially a salt thereof Reagent Compound of formula lil in which X stands, for example, for chlorine, bromine, iodine, mesyloxy or tosyloxy (a2) Halide, imidazolide or anhydride of an acid of formula II Compound of formula III in which X stands for hydroxy (a3) Free acid of formula ll Compound of formula Ill in which X stands for hydroxy (III especially = oxime) In process variant (a1), the term "salt" signifies, for example, an alkali metal salt (e.g. the sodium, potassium or lithium salt), an alkaline earth metal salt (e.g. the magnesium, calcium or barium salt), a salt of an organic base (e.g. a mono-, di- or trialkylammonium salt or a pyridinium salt) or the ammonium salt. The term "leaving group" used in connection with X preferably stands for chlorine, bromine, iodine, mesyloxy or tosyloxy.
The esterification of an acid of formula II or, preferably, a salt thereof, with a compound of formula Ill is preferably carried out in an inert solvent and at a temperature of about - 20"C to 1 00 C. A temperature range between 0 C and 40'C is especially preferred. Inert organic solvents are preferably used as the solvent. Preferred solvents are ethers (e.g. diethyl ether and tetrahydrofuran), chlorinated hydrocarbons (e.g. dichloromethane and chloroform) and dimethylformamide.
When a free acid of formula ll is used, the reaction is conveniently carried out in the presence of a base or an acid acceptor. For this purpose there can be used all customarily usable inorganic and organic acid-binding agents, preferably alkali metal and alkaline earth metal carbonates and bicarbonates and tertiary amines (e.g. triethylamine, dimethylaniline and pyridine).
The reaction according to process variant (a2) is conveniently carried out in an inert solvent such as an ether (e.g. diethyl ether), a hydrocarbon (e.g. n-hexane) or a chlorinated hydrocarbon (e.g. dichloromethane or chloroform) and at room temperature or an elevated temperature (e.g.
up to the reflux temperature of the reaction mixture). A temperature range between 0 C and 40"C is preferred and a temperature range between 1 0 C and 20"C is especially preferred.
When an acid halide of an acid of formula II is used, the reaction is conveniently carried out in the presence of an acid-binding agent. Inorganic bases (e.g. alkali metal and alkaline earth metal carbonates and bicarbonates) as well as organic bases (e.g. tertiary amines, especially triethylamine or pyridine) have been found to be suitable for this purpose. The acid halide is preferably the acid chloride.
In process variant (a3), the reaction is conveniently carried out in an inert organic solvent such as an ether (e.g. tetrahydrofuran) or a chlorinated hydrocarbon (e.g. dichloromethane or chloroform) and at a temperature between 0 C and 70"C. A temperature range between 1 0 C and 30"C is preferred. The reaction is conveniently carried out in the presence of an acid catalyst or a condensing agent such as, for example, sulphuric acid, hydrochloric acid, p toluenesulphonic acid, dicyclohexylcarbodiimide or carbonyldiimidazole.
Process variant (ay) is especially suitable where the compound of formula III is an oxime, i.e.
R5 signifies a group (d), m, n and p signify the number 0 and X signifies a hydroxyl group. An acid of fomula II is preferably reacted with an oxime of formula Ill in the presence of dicyclohexylcarbodiimide as the condensing agent. The acid is conveniently dissolved in an inert organic solvent such as a chlorinated hydrocarbon (e.g. dichloromethane, chloroform, carbon tetrachloride or trichloroethane), an ether (e.g. diethyl ether, diisopropyl ether or dioxan) or an aromatic hydrocarbon (e.g. benzene, toluene or xylene) and thereafter the oxime is suspended in the solution. The dicyclohexylcarbodiimide is likewise dissolved in the same solvent and added to the reaction mixture.The reaction is preferably carried out in a temperature range between 0 C and the boiling point of the reaction mixture, especially between room temperature and 50"C. The reaction is normally completed after about 2 hours.
In process variant (b), the term "leaving group" used in connection with Y signifies, for example, chlorine, bromine, iodine, mesyloxy or tosyloxy. The reaction is conveniently carried out in an inert organic solvent such as a hydrocarbon (e.g. benzene or toluene), an ether (e.g.
diethyl ether, dimethoxyethane or tetrahydrofuran) or hexamethylphosphoric acid triamide. The reaction temperature is not critical and the reaction is preferably carried out at a temperature between - 20"C and the reflux temperature of the reaction mixture, especially at a temperature between - 10"C and 30"C.
In each case the product obtained can be isolated and purified according to methods known per se.
Insofar as no planned synthesis for the isolation of pure isomers is carried out, the product normally occurs as a mixture of two or more isomers. The isomers can be separated according to methods known per se. If desired, they can also be manufactured by synthesis from corresponding optically active starting materials.
The starting materials of formulae 11, Ill, IV and V as well as reactive derivatives of the acids of formula II and alkali metal salts of the phenols of formula IV are either known or can be prepared in a manner known per se.
The compounds of formula I possess herbicidal properties and are especially suitable for the control of weed grasses, especially of slender foxtail (Alopecurus myosuroides) and types of millet such as, for example, cock's foot (Echinochloa crus-galli), great foxtail millet (Setaria faberii) and hair-like millet (Panicum capillare) in cereals, especially barley, oats and wheat cultivations, as well as in rice, cotton, soya, sugar beet and vegetable plantations. The compounds in accordance with the invention are particularly suitable for the control of weed grasses in cotton, soya, sugar beet and vegetable plantations.
In general, a concentration of 0. 1-6 kg of active substance of formula I per ha, preferably 0.6-2 kg of active substance of formula I per ha, is sufficient to produce the desired herbicidal effect.
The compounds of formula I are not only pre-emergence herbicides but also post-emergence herbicides.
The weed control compositions in accordance with the invention contain an effective amount of at least one compound of formula I, as defined above, as well as formulation adjuvants. The compositions conveniently contain at least one of the following formulation adjuvants: solid carrier substances; solvents or dispersion media; tensides (wetting and emulsifying agents); dispersing agents (without tenside action); and stabilizers. When using these and other adjuvants the compounds of formula I, namely the herbicidal active substances, can be converted into the usual formulations such as dusts, powders, granulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like.
The compounds of formula I are generally insoluble in water and can be formulated according to the methods which are usual for water-insoluble compounds using the respective formulation adjuvants. The manufacture of the compositions can be carried out in a manner known per se; for example, by mixing the respective active substance with solid carrier substances, by dissolution or suspension in suitable solvents or dispersion media, if necessary using tensides as wetting or emulsifying agents and/or dispersing agents, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.
As solid carrier substances there essentially come into consideration: natural mineral substances such as chalk, dolomite, limestone, aluminas and silicic acid and salts thereof (e.g.
siliceous earth, kaolin, bentonite, talc, attapulgite and montmorillonite); synthetic mineral substances such as highly dispersible silicic acid, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and nitrates, whereby such carrier substances can be present as powders or as granulates.
As solvents or dispersion media there essentially come into consideration: aromatics such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. petroleum fractions); alcohols such as butanol and glycol, as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solvents or dispersion media such as dimethylformamide, N-methyl-pyrrolidone and dimethyl sulphoxide, whereby such solvents preferably have flash points of at least 30"C and boiling points of at least 50"C, and water.
Among the solvents or dispersion media there also come into consideration so-called liquified gaseous extenders or carrier substances, these being products which are gaseous at room temperature and under normal pressure. Examples of such products are especially aerosol propellant gases such as halogenated hydrocarbons (e.g. dichlorodifluoromethane). If a weed control composition in accordance with the invention is present in the form of a pressurized pack, then a solvent is conveniently used in addition to the propellant gas.
The tensides (wetting and emulsifying agents) can be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.
The tensides can also be anionic compounds such as soaps; fatty sulphate esters (e.g. dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate); alkyl sulphonates, aryl sulphonates and fatty-aromatic sulphonates, such as alkylbenzene sulphonates (e.g. calcium dodecylbenzene sulphonate and butylnaphthalene sulphonates; and more complex fatty sulphonates, for example the amide condensation products of oleic acid and N-methyltaurine and the sodium sulphonate of dioctyl succinate.
Finally, the tensides can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.
As dispersing agents (without tenside action) there essentially come into consideration: lignin, sodium and ammonium salts of lignin sulphonic acids, sodium salts of maleic acid anhydride/diisobutylene copolymers, sodium and ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphite lyes.
As dispersing agents, which are especially suitable as thickening agents or anti-settling agents, there can be used, for example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.
Examples of suitable stabilizers are acid-binding agents (e.g. epichlorohydrin, phenyl glycidyl ether and soya epoxides); antioxidants (e.g. gallic acid esters and butylhydroxytoluene); UVabsorbers (e.g. substituted benzophenones, diphenylacrylonitrile acid esters and cinnamic acid esters); and deactivators (e.g. salts of ethylenediaminotetraacetic acid and polyglycols).
The weed control compositions in accordance with the invention can contain, in accition to the compounds of formula I, synergists and other active substances (e.g. insecticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for intensifying the activity or for broadening the spectrum of activity.
The weed control compositions in accordance with the invention generally contain between 0.1 and 99 weight percent, preferably between 5 and 75 weight percent, of one or more compounds of formula I as the active substance(s). They can be present, for example, in a form which is suitable for storage and transport. In such formulations (e.g. emulsifiable concentrates) the active substance concentration is normally in the higher range, preferably between 10 and 75 weight percent, especially between 25 and 50 weight percent. These formulations can subsequently be diluted, for example, with the same or different inert substances, to give active substance concentrations which are suitable for practical use, i.e. preferably about 0.1 to 10 weight percent, especially about 1 to 5 weight percent. The active substance concentrations can, however, also be smaller or greater.
Conveniently, in the weed control compositions in accordance with the invention the solid carrier substances are present in a concentration range between 1 and 99.9%, the solvents or dispersion media are present in a concentration range between 1 and 99.9%, the tensides are present in a concentration range between 1 and 20%, the dispersing agents are present in a concentration range between 1 and 20%, the dispersing agents as thickening or anti-settling agents are present in a concentration range between 0.1 and 5% and the stabilizers are present in a concentration range between 0.1 and 5%, these percentages referring to the total weight of the composition.
As mentioned above, the manufacture of the weed control compositions in accordance with the invention can be carried out in a manner known per se.
For the manufacture of pulverous preparations the active substance, i.e. at least one compound of formula I, can be mixed with solid carrier substance (e.g. by grinding together); or the solid carrier substance can be impregnated with a solution or suspension of the active substance and then the solvent or dispersion medium can be removed by evaporation, heating or sucking-off under reduced pressure. By adding tensides or dispersing agents such pulverous preparations can be made readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray compositions.
The compounds of formula I can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is dispersible in water, or they can be mixed with a solid pregranulated carrier substance to form a product in the form of a granulate.
If desired, the compounds of formula I can be dissolved in a water-immiscible solvent such as, for example, a high-boiling hydrocarbon, which conveniently contains a dissolved emulsifying agent, so that the solution becomes self-emulsifying upon addition to water. Alternatively, the active substance can be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concentration. Moreover, the active substance can be dissolved in a solvent and thereafter the solution can be mixed with an emulsifying agent. Such a mixture can likewise be diluted with water to the desired concentration. In this manner there are obtained emulsifiable concentrates or ready-for-use emulsions.
The use of the weed control compositions in accordance with the invention can be carried out according to usual application methods such as sprinkling, spraying, dusting, pouring or scattering. The method in accordance with the invention for the cqntrol of weeds comprises treating the locus to be protected against weeds and/or the weeds with a compound in accordance with the invention or with a weed control composition in accordance with the invention.
The following Examples illustrate the present invention: I. Manufacture of the active substances of formula I: Example I 0.47 g of pyridine is added dropwise to a solution, cooled at 5 C, of 1.72 g D-2-[p-(α,α,α- trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 0.58 g or 2-isopropylidineaminooxy-ethanol in 40 ml of benzene. The mixture is stirred at room temperature for 1 hour and subsequently evaporated to dryness under reduced pressure. Thereafter, the residue is dissolved in diethyl ether/n-hexane (1:1) and the solution is extracted with water and dilute sodium bicarbonate solution, dried over a drying agent and finally evaporated to dryness.
The liquid residue is purified by chromatography on silica gel with acetone/n-hexane (1:7).
There is obtained 2-isopropylideneaminooxy-ethyl D-2-[α,α,α-trifluoro-p-tolyloxy)phenoxy]-pro- pionate; n20D = 1.5088; [α]22D = ~ 13.9 (c = 1.0% in CHCl3).
ln an analogous manner, from D-2-[p-(α,α,α-trifluoro-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-acetamide there is obtained acetamidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionate; m.p. 103-105 C; [α]22D = 13.5 9c = 1.1% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-chloroacetamide there is obtained chloroacetamidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy] propionate; m.p. 98-99 C; [α]22D=19.8 (c = 0.7% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propional chloride and N-hydroxymethyl-trichloroacetamide there is obtained trichloroacetamidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phe noxylpropionate; n2g= 1.5320; (a]20= + 14.8 (c=0.6% in CHCI3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-methanesulphonamido-ethanol there is obtained 2-methanesulphonamido-ethyl D-2-[p-(α,α,α-trifluoroo-p-tolyloxy)phe- noxy]-propionate; m.p. 65-68 C; [α]22D= + 24.6 (c = 1.1% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-succinimide there is obtained succinimidomethyl D-2-[p-α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propion- ate; m.p. 74-76éC; [α]22D = + 13.5 (c = 1.3% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethylphthalimide there is obtained phthalimidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-pro- pionate: m.p. 99-100 C; [α]22D = 4.9 (c = 0.7% on CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxyphosphinylmethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]- propionate; n20D = 1.5008; [α]22D = 27.5 (c = 1.0% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-diethoxyphosphinylethanol there is obtained 2-diethoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]- propionate; n20D = 1.5001; [α]20D = +20.7 (c = 0.7% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 1-diethoxyphosphinyl ethanol there is obtained 1-diethoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]- propionate; n20D= 1.4963; [α]22D = + 20.3 (c = 1.3% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 1 -diethoxyphosphinyl-n- butanol there is obtained 1 -diethoxyphosphinyl-n-butyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phe- noxy]-propionate; n20D= 1.4945: [α]22D = + 23.0 (c = 1.4% in CHCl3); from D-2-[p-(α,α,α-trifluro-p-tolyloxy)phenoxy]-propionyl chloride and α-diethoxychosphinyl- benzyl alcohol there is obtained a-diethoxyphosph inyl-benzyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)- phenoxy]-propionate; n2,0= 1.5228; [α]22D= + 25.5 (c = 0.7% in CHCl9); from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and 2-isopropylideneaminooxy-ethanol there is obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propion- ate; [α]22D = + 12.6 (c = 1.2% in CHCl3);; from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and 2-methanesulphoamido-ethanol there is obtained 2-methanesulphonamido-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate; m.p. 84-87'C; [aY2= + 23.2" (c = 1.0% in CHCl3); from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and N-hydroxymethyl-succinimide there is obtained succinimidomethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate; [α]22D= + 11.5" (c = 0.8% in CHCl3); from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxyphosphinylmethyl D-2-[p-(p-iodophenoxy)phenoxy-propionate; [α]22D= + 23.7 (c = 1.7% in CHCl3);; from D-2-[p-(p-iodophenoxy)phenoxy)-propionyl chloride and 2-diethoxyphosphinyl-ethanol there is obtained 2-diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate; [α]22D = + 19.7% (c = 1.3% in CHCl3);' from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl chloride and 2-isopropylideneaminooxy-ethanol there is obtained 2-isopropyl ideneaminooxy-ethyl D-2-[p-(o- chloro-p-iodophenoxy)phenoxy]-propionate; [α]20d = + 11.7" (c = 0.9% in CHCl3); from D-2-[p-(o-chloro-p-iodophenoxy]-propionyl chloride and 2-methanesulphonamido-ethanol there is obtained 2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-pro- pionate; [α]20D - + 19.4 (c = 0.8% in CHCl3);; from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxyphosphinylmethyl D-2-[p-(o-chloro-p- iodophenoxy)phenoxy]propionate; [ai20= + 19.7" (c= 1.6% in CHCI3); from D-2 chloride and dibutoxyphosphinylmethanol there is obtained dibutoxyphosphinyl methyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]- propionate; n20D= 1.4932; [α]20D = + 23.2 (c = 0.60% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride ethanol there is obtained 1 -diphenoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]- propionate; n20D = 1.5449; [α]22D = ~ 7.3 (c = 1.1% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 1-isopropylideneaminooxy-2-propanol there is obtained 1 -isopropylideneam i nooxy-2-propyl D-2-[p-(a,a, a-trifl uoro-p- tolyloxy)phenoxy]-propionate; n20D = 1.5026; [α]22D = + 19.0 (c = 1.1% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 1 -isopropylideneaminooxy-2-butanol there is obtained 1 -isopropylideneaminooxy-2-butyl D-2-[p-(α,α,α-trifluoro-p- tolyloxy)phenoxy]-propionate; n2,0= 1.5023;[α]22D= + 20.7" (c = 1.0% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-isopropylideneami nooxy- 1 -phenyl-ethanol there is obtained 2-isopropylideneaminooxy- l-phenylethyl D-2-[p-(a,a,atrifluoro-p-tolyloxy)phenoxy]-propionate; [α;]22D= + 19.8 (c = 0.9% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-(2-butylideneaminooxy)-ethanol there is obtained 2-(2-butylideneami nooxy)-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl phenoxy]-propioate; n20D = 1.5072; [α]22D= + 13.7 (c = 1.1% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-(a-methylbenzyl ide- neaminooxy)-ethanol there is obtained 2-(a-methylbenzylideneaminooxy)-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionate; n20D= 1.5456; [α]22D = + 7.6é (c = 1.0% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-cyclohexylideneaminooxy-ethanol there is obtained 2-cyclohexylideneaminooxy-ethyl D-2-[p-(a,a,a-trifluoro-p-tolylox- y)phenoxy]-propionate; n20D= 1.5201; [α']20D= + 11.7 (c = 1.1% in CHCl3).
Example 2 3.0g of D-2-[p-α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propionic acid are suspended in 1 Oml of dichloromethane and 1.3g of ethylacetoacetate oxime are added at room temperature. A solution of 1 .9g of dicyclohexylcarbodiimide in 1 Oml of dichloromethane is added dropwise to the suspension during 10 minutes, the temperature of the mixture thereby rising to 40"C. The mixture is stirred at room temperature for a further 2 hours and subsequently filtered. The filtrate is evaporated to dryness under reduced pressure. There is obtained ethyl 3-[D-2-[p-(a,a,a- trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino]-butyrate; [α]20D= + 39.8 (c = 1.0% in CHCl3).
In an analogous manner, from D-2-[p-α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and l,l,l-trifluoroacetone oxime there is obtained D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionic acid l,l,l-trifluoroacetone oxime ester; [aJ20= + 39.5" (c= 1.0% in CHCI3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and l-hydroxyimino-diethyl ether there is obtained ethyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)]-propionoxy]-acetimidate; n20D= 1.5087; [α]22D= + 53 (c = 0.9% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionic acid and n-butyl (I-hydroxyiminoethyl) ether there is obtained n-butyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxyl-prnpionoxy)-acetimi- date; n20D= 1.5036; [α]22D= + 49.87 (c = 1.2% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl [I-hydroxyimino-n-butyl) ether there is obtained ethyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propionoxy]-n-butyri- midate; n20D= 1.5058; [α]20D= + 52.58 (c = 1.0% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and methoxyacetone oxime there is obtained D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid methoxyacetone oxime ester; (aP0= + 48.772 (c = 1.9% in CHCI3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and diacetone monoxime there is obtained D-2-[p-(a,a,a-trifluoro-p-tolyloxy) phenoxy]-propionic acid diacetone monoxime ester; [α]20D= + 30.7" (c = 1.0% in CKCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl pyruvate oxime there is obtained ethyl 2-[D-2[p-(α,α,α-trifluoro-p-tolyloxy))phenoxy-propionic 2g= + 45.01%) = 2.0% in CHCl3); from D-2-[p(α,α,α;-trifluoro-p-tolyloxy)phenoxy-propionic acid and ethyl o-methyl-acetoacetate oxime there is obtained ethyl 2-methyl-3-[D-2-[p-(α,αα-trifluoro-p-tolyloxy)-phenoxy]-propionoxy- imino]-butyrate;[α]20D= + 41.07 (c = 0.9% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl levulinate oxime there is obtained ethyl 4-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionoxy- [α]20D= + 37.4 (c = 1.2% in CHCl3; from D-2-[p-(o-chloro-p-trifluoromethyl-phenoxy) phenoxyl]-propionic acid and 2-isopropylideneaminooxy-ethanol there is obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro-p-trifluoro- methyl-phenoxy) phenoxyi-prnpionate; [α]20D= + 12.3" (c = 0.69% in CHCl3); from D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionic acid and cyclopentanone oxime there is obtained D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxyj-propionic acid cyclopentanone oxime ester; [α]20D= + 40.8 (c = 1.0% in CHCl3).
Example 3 A solution of 1.799 of D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid, 1.30g of 1diethoxy-phosphinyl-cyclohexanol and 0.069 of 4-dimethylamino-pyridine in 20ml of dichloromethane is treated at room temperature with 1.1 3g of dicyclohexylcarbodiimide and the mixture is stirred for 24 hours. The mixture is then evaporated to dryness under reduced pressure, the residue is dissolved in diethyl ether/n-hexane (1:1) and the insoluble part of the residue is filtered off under suction. Subsequently the filtrate is washed twice with 30ml of 5% acetic acid each time and three times with 30 ml of water each time, dried over a drying agent and evaporated to dryness.The liquid residue is purified by chromatography on silica gel with dich!oromethane/ diethyl ether (1:1). There is obtained 1-diethoxy-phosphinyl-cyclohexyl D-2-[p- (ata,a-trifluoro-p-tolyloxy)-phenoxy]-propionate; n2g= 1.5073.
In an analogous manner, from D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid and 2-dimethoxyphosphinyl-2-propanol there is obtained 2-dimethoxypghosphinyl-2-propyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phe- noxy]-propionate; n20D= 1.5019; [α]22D= + 7.6 (c = 1.2% in CHCl3).
Example 4 A mixture of 1.89 g of D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid, 1.43 g of 3diethoxyphosphinylpropyl bromide, 0.40 g of potassium carbonate and 50 ml of absolute acetone is heated at reflux for 15 hours. Thereafter, the mixture is eveporated to dryness under reduced pressure and the residue is dissolved in diethyl ether. The solution is washed twice with 25 ml of water each time and extracted twice with 25 ml of sodium bicarbonate solution each time, dried over a drying agent and evaporated to dryness.
The liquid residue is purified by chromatography on silica gel with dichloromethane. There is obtained 3-diethoxyphosphinyl-propyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionate; n2,0= 1.4986; [α]22D= + 20.52" (c = 0.9% in CHCl3).
In an analogous manner, from D-2-[p-(p.iodophenoxy) phenoxyj-prnpionic acid and 3-diethoxyphosphinylpropyl bromide there is obtained 3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy) phenoxyj-propionate; [aj%2= + 20.4" (c = 1.2% in CHCl3).
II. Formulation Examples: Example 5 For the manufacture of an emulsifiable concentrate the following ingredients are mixed with one another: Compound of formula 1 500 g Mixture of condensation products of an alkylphenol and ethylene oxide and calcium dodecylbenzenesulphonate 100 g Epoxidated soya oil with an oxirane oxygen content of about 6% 25 g Butylated hydroxytoluene 10 g The mixture is made up to 1 litre with xylene.
The thus-obtained concentrate emulsifies spontaneously in water. The resulting emulsion is suitable as a ready-for-use spray liquor.
Example 6 For the manufacture of an emulsifiable concentrate the following ingredients are mixed with one another: Compound of formula 1 250 g/l N-Methyl-2-pyrrolidone 300 g/i Emulsifier A') 1 00 g/l Emulsifier B2) 25 g/l Solvent mixture of alkylbenzenes to 1000 ml "Emulsifier A: Emulsifier consisting of 60 parts of a block polymerisate of ethylene oxide and proplyene oxide, 20 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 20 parts of a solvent mixture of isobutanol and C10-alkylbenzenes.
2)Emulsifier B: Mixture of 70 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 30 parts of a solvent mixture of isobutanol and C10-alkylbenzenes.
The thus-obtained concentrate emulsifies spontaneously in water. The resulting emulsion is suitable as a ready-for-use spray liquor.
111. Biological Results: Example 7 The formulation of Example 6 is sprayed on the test weeds (Lolium multiflorum or Bromus inermis) in fixed dilutions with water containing 0.5 volume percent of Nonoxynol (condensation product of nonylphenol and ethylene oxide). The spraying is carried out by means of a logarithmic spray apparatus which enables the concentration of the active substance to be halved automatically after fixed intervals. The spray volume amounts to 500 1 /ha. 33 days after the spraying the weeds are investigated for the effect which has occurred, i.e. there is determined the dosage at which a satisfactory control of the weeds is achieved. The results are compiled in Table I hereinafter.
Table 1 Dosage (g of active substance/ha) Active substance of Lolium Bromus formula I multiflorum inermis Ethyl N-[D-2-[p-(a,a,a- -trifluoro-p-tolyloxy)- phenoxy]-propionoxy]-n -butyrimidate 165 165 n-Butyl N-[D-2-[p-(a,a,a- -trifluoro-p-tolyloxy)phenoxy]-propionoxy] -acetimidate 1 25 220 Example 8 The active substance is tested in the formulation of Example 6. Shortly before the beginning of the test, it is diluted to the desired concentration with water containing 0.5 volume percent of Nonoxynol as the wetting agent.
The test weeds (Oryza sativa) in the 2 leaf stage are sprayed in a greenhouse with the thus formulated active substance. Subsequently, a 16 hours day is simulated by means of mercury lamps. Three weeks after the spraying the weeds are investigated for the effect which has occurred, i.e. the percentage necrosis is determined, with a 100% necrosis corresponding to a complete destruction of the weeds. The results are compiled in the Table II hereinafter.
Table II Active substance of Dosage % Necrosis formula I g/ha (Oryza sativa) D-2-[p-(α,α,α-Trifluoro- -p-tolyloxy) phenoxy] propionic acid methoxy acetone oxime ester 150 90

Claims (23)

1. Compounds of the general formula
wherein R' signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen, chlorine, bromine or iodine, R3 signifies hydrogen or C, 4-alkyl, R4 signifies hydrogen; C, 4-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which they are attached can also form a C58- cycloalkane ring which, if desired, can be substituted with 1 to 3 C, 4-alkyl groups, m, n and p signify the number 0 or 1 and R5 signifies one of the following groups (a) - (f):: -NHCO-R6 (a) -NHSO2-R7 (b)
whereby in the above formulae of the groups (a) - (f) R6 signifies hydrogen; C1-6-alkyl; C, 4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and / or nitro, R7 signifies C, 6-alkyl;; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R8 and R9 stand for hydrogen or together signify a bond, trimethylene, tetramethylene, 2butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R11 signifies trifluoromethyl, C1-6-alkoxy, C1-6-alkoxy-C1-4-alkyl, C2-7alkanoyl, C2 7-alkoxycarbonyl or C2-7-alkoxycarbonyl-C1-4-alkyl, or R10 and R11 together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be substituted with 1 to 3 C1 4alkyl groups and/or 1 C, 4-alkoxy group, whereby, where R10, R"and the carbon atom form an optionally substituted cyclopentane ring, R' is chlorine, bromine or trifluoromethyl, R12 signifies hydrogen or C1-8-alkyl and R13 signifies C, 6-alkyl;; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, or R12 and R'3 together with the carbon atom to which they are attached form a C5 7-cycloalkane ring, and R'4 and R15 signify C1 6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 represents a group (d), m, n and p signify the number 0; when R5 represents a group (e), m signifies the number 0 and n and p signify the number 1; and when R5 represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1.
2. Compounds according to claim 1, wherein R1 signifies iodine or trifluoromethyl.
3. Compounds according to claim 1 or claim 2, wherein R2 signifies hydrogen or chlorine.
4. The D-isomers of the compounds according to any one of claims 1 to 3.
5. Succinimidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionate.
6. Ethyl N [D- 2-[p-(a, a, a-trifluoro-p-tolyloxy)-phenoxy-propionoxy]-acetim idate.
7. n-Butyl N-[D-2-[p-(α,α,α-trifluoro-p-tolyoxy) phenoxy]-propionoxy]-aceti midate.
8. 2-lsopropylideneaminooxy-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionate.
9. Diethoxyphosphinylmethyl D-2-[p-(ata,a-trifluoro-p-tolyloxy)phenoxy]-propionate.
10. A compound according to claim 1, selected from: Acetamidomethyl D-2-[p-(α,α,α- trifluoro-p-tolyloxy) phenoxy]-propionate, chloroacetamidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, trichloroaceta m idomethyl D-2-(p-(a, a, a-trifluoro-p-tolyloxy) phenoxy]-propionate, 2-methanesulphomanido-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, phthalimidomethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 2-diethoxyphosphinyl-ethyl D-2-(p-(a, α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1-diethoxyphosphinyl-ethyl D-2-[p-(α;,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1-diethoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, α-diethoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, ethyl 3-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino]-butyrate, D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxyj-prnpionic acid 1 ,1,1 -trifluoroacetone oxime ester, ethyl N-(D-2-[p-(a, a, α;-trifluoro-p-tolyloxy)-phenoxy]-propionoxy]-n-butyrimidate, D-2-[p-(a,a,a-trifluoro-p-tolyloxy) phenoxy]-propionic acid methoxyacetone oxime ester, D-2-[p-(a,a,a-trifluoro-p-tolyloxy) phenoxyl-propionic acid diacetone monoxime ester, ethyl 2-[D-2-[p-)α,α,α-trifluoro-p-tolyloxy)-phenoxyl]-propionoxyimino]-propionate, ethyl 2-methyl-3-[D-2-(p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionoxyimino]-butyrate, ethyl 4-[D-2-[p-(α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino]-n-valerate, 2-isopropylideneaminooxy-ethyl D-2-[p-(α-chloro-p-trifluoromethyl-phenoxy]-propion- ate, D-2-[p-(α,α,α;-trifluoro-p-tolyloxy) phenoxyl-propionic acid cyclopentanone axime ester, 1-diethoxyphosphinyl-cyclohexyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 2-dimethoxyphosphinyl-2-propyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate and 3-diethoxyphosphinyl-propyl D-2-[p-(a, a, α-trifluoro-p-tolyloxy) phenoxy]-propionate.
11. A compound according to claim 1, selected from: 2-lsopropylideneaminooxy-ethyl D-2-[p-(p-iodophenoxy) phenoxy]-propionate, 2-methanesulphonamido-ethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, succinimidomethyl D-2-[p-(p-iodophenoxy) phenoxy]-propionate.
diethoxyphosphinylmethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, 2-diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, 2-isopropylidencaminooxy-ethyl D-2-[p-(α-chloro-p-iodophenoxy) phenoxy]-propionate, 2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionate, diethoxyphosphinylmethyl D-2-[p-(o-chloro-p-iodophenoxy) phenoxyl-propionate, dibutoxyphosphinylmethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1-diphenoxyphosphinyl-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1-isopropylideneaminooxy-2-propyl D-2-[p-(αp;,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1-isopropylideneaminooxy-2-butyl D-2-[p-(α,α;,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 1 -isopropyl ideneaminooxy-1 -phenylethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxyj-prnpion- ate, 2-(2-butylideneaminooxy)-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 2-(α-methylbenzylideneaminooxy)-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate, 2-cyclohexylideneaminooxy-ethyl D-2-[p-(α,α,α-trifluoro-p-tolyloxy) phenoxy]-propionate and 3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate.
12. A compound according to any one of claims 1 to 10 as a weed control agent.
13. A compound according to claim 11 as a weed control agent.
14. A weed control composition, which contains an effective amount of at least one compound of the general formula
wherein R' signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen, chlorine, bromine or iodine, R signifies hydrogen or C1-4-alkyl, R4 signifies hydrogen; C1-4-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, whereby R and R4 together with the carbon atom to which they are attached can also form a C5-a-cycloalkane ring which, if desired, can be substituted with 1 to 3 C1-4-alkyl groups, m, n and p signify the number 0 or 1 and R5 signifies one of the following groups (a) - (f):
whereby in the above formulae of the groups (a) - (f) R6 signifies hydrogen;C1-6-alkyl-C1-4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro R7 signifies C, 6-alkyl; or phenyl, optionally substituted with halogen, C1-4 alkyl and/or nitro R8 and R9 stands for hydrogen or together signify a bond, trimethylene, tetramethylene, 2butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R11 signifies trifluoromethyl, C1-6-alkoxy, C1-6-alkoxy-C1-4-alkyl, C2-7alkanoyl, C2 7-alkoxycarbonyl or C2-7-alkoxycarbonyl-C1-4-alkyl, or R10 and R11 together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be substituted with 1 to 3 C1-4-alkyl groups and/or 1 C, 4-alkoxy group, whereby, where R10,R11 and the carbon atom form an optionally substituted cyclopentane ring, R1 is chlorine, bromine or trifluoromethyl, R12 signifies hydrogen or C1-6-alkyl and R13 signifies C, 6-alkyl; or phenyl, optionally substi-tuted with halogen, C1-4-alkyl and/or nitro, or R12 and R13 together with the carbon atom to which they are attached form a C5 7-cycloalkane ring and R14 and R15 signify C1-6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 represents a group (d), m, n and p signify the number 0; when R5 represents a group (e), m signifies the number 0 and n and p signify the number 1; and when R5 represents a group (f), m and p signify the number 0 and 1 and n signifies the number 1, as well as formulation adjuvants.
15. A weed control composition according to claim 14, which contains an effective amount of one of the compounds set forth in claims 5 to 9.
16. A process for the manufacture of compounds of the general formula
wherein R' signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen, chlorine, bromine or iodine, R3 signifies hydrogen or C1-4-alkyl, R4 signifies hydrogen; C1-4-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which they are attached can also form a C5 8-cycloalkane ring which, if desired, can be substituted with 1 to 3 C1-4-alkyl groups, m, n and p signify the number 0 or 1 and R5 signifies one of the following groups (a) . (f): -NHco-R6 (a) -NHSO2-R7 (b)
whereby in the above formulae of the groups (a) - (f) R6 signifies hydrogen;C1-6-alkyl; C, 4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R7 signifies C1-6-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R8 and R9 stand for hydrogen or together signify a bond, trimethylene, tetramethylene, 2-butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R signifies trifluoromethyl, C1-6-alkoxy, C1-6-alkoxy-C1-4-alkyl, C2-7alkanoyl, C27-alkoxycarbonyl or C2-7-alkoxycarbonyl-C1-4-alkyl, or R'D and R11 together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be substituted with 1 to 3 C1 4-alkyl groups and/or 1 C, 4-alkoxy group, whereby, where R' , R11 and the carbon atom form an optionally substituted cyclopentane ring, Rl is chlorine, bromine or trifluoromethyl, R12 signifies hydrogen or C1-6 -alkyland R13 signifies Cl 6-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, or R12 and R'3 together with the carbon atom to which they are attached form a C5-7-cycloalkane ring, and R14 and R'5 signify C1-6-alkylo or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 represents a group (d), n, n and p signify the number 0; when R5 represents a group (e), m signifies the number 0 and n and p signify the number 1; and when R5 represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1, which process comprises (a) reacting an acid of the formula
wherein R' and R2 have the significance given earlier in this claim, or a reactive derivative thereof, with a compound of the formula
wherein R3, R4, R5, m, n and p have the significance given earlier in this claim and X signifies a leaving group, or (b) reacting a phenol of the formula
wherein R' and R2 have the significance given earlier in this claim, or an alkali metal salt thereof, with a compound of the formula
wherein R3, R4, R5, m, n and p have the significance given earlier in this claim and Y signifies a leaving group.
1 7. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of one of the compounds set forth in claims 1 to 10 or of a composition set forth in claim 14 or claim 1 5.
1 8. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of one of the compounds set forth in claim 11.
19. The use of one of the compounds set forth in claims 1 to 10 or of a composition set forth in claim 14 or claim 1 5 for the control of weeds.
20. The use of one of the compounds set forth in claim 11 for the control of weeds.
21. A compound of formula I according to claim 1, whenever produced by a process according to claim 1 6 or by an obvious chemical equivalent thereof.
22. A weed control composition according to claim 14, substantially as described herein with reference to Example 5 or 6.
23. A process according to claim 16, substantially as described with reference to any one of Examples 1 to 4.
GB8138135A 1980-12-18 1981-12-17 Herbicidal propionic acid esters Withdrawn GB2091248A (en)

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AU (1) AU7846381A (en)
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ES (1) ES508104A0 (en)
FI (1) FI814059L (en)
GB (1) GB2091248A (en)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801272A (en) * 1993-06-01 1998-09-01 Basf Aktiengesellschaft Preparation of mixtures of (R)- and (S)-2-(4-alkanoylphenoxy)- or (R)- and (S)-2-(4-aroylphenoxy)propionic esters
WO1999009994A1 (en) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft Use of cycloalcane-phosphonic acid esters for treating mental disorders and depressions
CN100412078C (en) * 2004-02-26 2008-08-20 华中师范大学 Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5832890A (en) * 1981-08-21 1983-02-25 Sumitomo Chem Co Ltd Phosphonic ester derivative, its preparation, hebicide containing the same as active ingredient
CA1246571A (en) * 1983-04-06 1988-12-13 Georg E. Frater Propionic acid esters
CA1249993A (en) * 1983-10-18 1989-02-14 Paul Winternitz Aryloxyphenoxy(acyloxy)alkyloximes, -carbamates and-phosphonates
DK160818C (en) * 1983-12-30 1991-10-07 Hoffmann La Roche N-RING containing glycerol derivatives, processes for their preparation, their use for the preparation of a platelet activation factor inhibitor, and drugs containing such a compound

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Publication number Priority date Publication date Assignee Title
DE2617804C2 (en) * 1976-04-23 1985-01-24 Hoechst Ag, 6230 Frankfurt 2- (4-Phenoxy phenoxy) propionic acid derivatives and their use as herbicides
US4200587A (en) * 1977-11-28 1980-04-29 Hoffmann-La Roche Inc. 2-[P-(p-Substituted phenoxy)phenoxy]propionyl oximes
DE2860453D1 (en) * 1978-01-10 1981-02-26 Ciba Geigy Ag Herbicidally active 4-(p-phenoxy-phenoxy)-alpha-propionic acid alkoxyalkylamides, process for their preparation, herbicidal agents containing them and their use
DE2839828C2 (en) * 1978-09-13 1983-09-15 Vsesojuznyj naučno-issledovatel'skij institut fitopatologii, p/o B. Vjazemy, Odincovskij rayon, Moskovskaja oblast' 0,0-Diaryl-1-acyloxy-2,2,2-trichloroethylphosphonate and fungicides based thereon
CA1142540A (en) * 1979-12-12 1983-03-08 Georg Frater Propionic acid esters
ZA811357B (en) * 1980-03-10 1982-03-31 Hoffmann La Roche Oxime esters

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801272A (en) * 1993-06-01 1998-09-01 Basf Aktiengesellschaft Preparation of mixtures of (R)- and (S)-2-(4-alkanoylphenoxy)- or (R)- and (S)-2-(4-aroylphenoxy)propionic esters
WO1999009994A1 (en) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft Use of cycloalcane-phosphonic acid esters for treating mental disorders and depressions
CN100412078C (en) * 2004-02-26 2008-08-20 华中师范大学 Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof

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EP0054715A2 (en) 1982-06-30
ES8302631A1 (en) 1983-02-01
EP0054715A3 (en) 1982-09-22
AU7846381A (en) 1982-06-24
CA1156663A (en) 1983-11-08
DK561581A (en) 1982-06-19
NO814332L (en) 1982-06-21
IL64523A0 (en) 1982-03-31
FI814059L (en) 1982-06-19
ES508104A0 (en) 1983-02-01

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