IE51432B1 - 2-fluoroalkanecarboxylic acid compounds,their preparation,herbicides containing these compounds,and their use - Google Patents

Abstract

1. Claims for the Contracting States : BE, CH, LI, DE, FR, GB, IT, LU, NL, SE A 2-fluoroalkanecarboxylic acid compound of the general formula where R**1 is aryl or hetaryl optionally substituted by halogen, nitro, straight-chain alkyl of 1 to 14 carbon atoms, branched alkyl of 3 to 14 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, alkoxy or alkylthio of 1 to 5 carbon atoms, haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl of up to 4 carbon atoms and up to 9 halogen atoms, formyl, cyano or thiocyanato, alkoxycarbonyl, dialylketo, alkylcarbonyl, alkylcarbamyl, dialkylcarbamyl, acylamino or alkylaminosulfonyl of 2 to 10 carbon atoms, alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, phenyl or phenylcarbonyl of 6 to 11 carbon atoms, aryloxy, arylalkoxy or arylazo optionally substituted by chlorine or trifluoromethyl, arylthio, arylsulfinyl or arylsulfonyl, arylalkyl, straight-chain alkenyl of 2 to 6 carbon atoms or branched alkenyl of 3 to 7 carbon atoms, straight-chain alkynyl of 2 to 4 carbon atoms or branched alkynyl of 3 to 6 carbon atoms, or a fused-on benzo, benzofuran or pyridino, R**2 and R**3 , independently of one another, are hydrogen, aryl or hetaryl optionally bearing the same substituents as in the case of R**1 ; alkyl optionally substituted by chlorine, bromine, fluorine, nitro, cyano, methoxy or ethoxy ; cycloalkyl optionally substituted by chlorine or trifluoromethyl ; or aralkyl, X is oxygen or sulfur, R**4 is hydroxyl or is OR**5 , SR**5 or see diagramm : EP0044979,P26,F2 where R**5 is aryl or hetaryl optionally bearing the same substituents as in the case of R**1 ; alkyl optionally substituted by chlorine, fluorine, bromine, methoxy, ethoxy, butoxy, cyclohexoxy, methylmercapto or ethylmercapto ; alkenyl optionally substituted by chlorine ; alkynyl optionally substituted by chlorine ; cycloalkyl ; cycloalkenyl ; alkanonyl ; or hetarylalkyl, R**6 is hydrogen or has one of the meanings given for R**5 , except optionally substituted n-anilino, R**7 , independently of R**6 , has one of the meanings given for R**5 or is hydroxyl, alkoxy, alkylthio, cyano, cyanoalkyl or see diagramm : EP0044979,P26,F3 where R**8 and R**9 , independently of one another, are hydrogen ; aryl optionally bearing the same substituents as in the case of R**1 ; alkyl, and R**6 and R**7 together with the adjacent nitrogen can also be a heterocyclic radical which is optionally substituted by methyl and may or may not contain one or more double bonds and one or more hetero atoms in addition to the nitrogen, or a salt of this compound. 1. Claims for the Contracting State : AT A herbicide containing a 2-fluoroalkanecarboxylic acid compound of the general formula see diagramm : EP0044979,P26,F4 where R**1 is aryl or hetaryl optionally substituted by halogen, nitro, straight-chain alkyl of 1 to 14 carbon atoms, branched alkyl of 3 to 14 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, alkoxy of alkylthio of 1 to 5 carbon atoms, haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl of up to 4 carbon atoms and up to 9 halogen atoms, formyl, cyano or thiocyanato, alkoxycarbonyl, dialkylketo, alkylcarbonyl, alkylcarbamyl, dialkylcarbamyl, acylamino or alkylaminosulfonyl of 2 to 10 carbon atoms, alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, phenyl of phenylcarbonyl of 6 to 11 carbon atoms, aryloxy, arylalkoxy or arylazo optionally substituted by chlorine or trifluoromethyl, arylthio, arylsulfinyl or arylsulfonyl, arylalkyl, straight-chain alkenyl of 2 to 6 carbon atoms or branched alkenyl of 3 to 7 carbon atoms, straight-chain alkynyl of 2 to 4 carbon atoms or branched alkynyl of 3 to 6 carbon atoms, or a fused-on benzo, benzofuran or pyridino, R**2 and R**3 , independently of one another, are hydrogen ; aryl or hetaryl optionally bearing same substituents as in the case of R**1 ; alkyl optionally substituted by chlorine, bromine, fluorine, nitro, cyano, methoxy or ethoxy ; cycloalkyl optionally substituted by chlorine or trifluoromethyl ; or aralkyl, X is oxygen or sulfur, R**4 is hydroxyl or is OR**5 , SR**5 or see diagramm : EP0044979,P27,F3 where R**5 is aryl or hetaryl optionally bearing the same substituents as in the case of R**1 ; alkyl optionally substituted by chlorine, fluorine, bromine, methoxy, ethoxy, butoxy, cyclohexoxy, methylmercapto or ethylmercapto ; alkenyl optionally substituted by chlorine ; alkynyl optionally substituted by chlorine ; cycloalkyl ; cycloalkenyl ; alkynonyl ; or hetarylalkyl, R**6 is hydrogen or has one of the meanings given for R**5 , except optionally substituted n-anilino, R**7 , independently of R**6 , has one of the meanings given for R**5 or is hydroxyl, alkoxy, alkylthio, cyano, cyanoalkyl or see diagramm : EP0044979,P27,F4 where R**8 and R**9 , independently of one another, are hydrogen ; aryl optionally bearing the same substituents as in the case of R**1 ; alkyl, and R**6 and R**7 together with the adjacent nitrogen can also be a heterocyclic radical which is optionally substituted by methyl and may or may not contain one or more double bonds and one or more hetero atoms in addition to the nitrogen, or a salt of this compound.

Description

The present invention relates to novel fluorinated aryloxycarboxylic and hetaryloxycarboxylic acid compounds having a herbicidal action, to herbicides which contain these compounds, to methods for controlling un5 desired plant growth by use of these compounds, and to processes for the preparation of the compounds.

The use of phenoxyalkanecarboxylic acid derivatives, for example the dimethylamine salt of 2-methyl-4chlorophenoxy-a-propionic acid (German Published Applica10 tion DAS 1,064,286) or the dimethylamine salt of 2,4dichlorophenoxy-a-propionic acid (German Patent 1,542,79) as herbicides is known.

The discovery, in 1942, of the herbicidal action of phenoxyalkanecarboxylic acids made it possible to control numerous broad-leaved weeds in crop plants of the Gramineae'family such as cereals, Indian com and rice. Other phenoxy-fatty acid derivatives having special properties came to be used later, either as individual products or as components of mixtures.

-° The literature dealing with the chemistry, the fields of use, and the advantages and disadvantages of the known compounds of this class, including their salts and esters, is extensive (Wegler, R. - Chemie der Pflanzenschutz- und Schadlingsbekfimpf ungsmittel, Volume , 1977). In spite of the world-wide use of phenoxyalkanecarboxylic acids, the fact that such use constitutes a certain hazard to the crop plant cannot be overlooked. 5143« The user seeks to minimize this hazard by applying the active compounds very precisely, and at times at which the crop plant is in certain less sensitive stages of growth.

We have found that 2-fluoroalkanecarboxylic acid compounds of the general formula ' 2 R-O-C-C < \ F '4 r R where R1 is aryl or hetaryl optionally substituted by halogen, nitro, straight-chain alkyl of 1 to 14 carbon atoms, branched alkyl of 3 to 14 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, alkoxy or alkylthio of 1 to 5 carbon atoms, haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl of up to 4 carbon atoms and up to 9 halogen atoms, formyl, cyano or thiocyanato, alkoxycarbonyl, dialkylketo, alkylcarbonyl, alkylcarbamyl, dialkylcarbamyl, acylamino or alkylaminosulfonyl of 2 to 10 carbon atoms, alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, phenyl or phenylcarbonyl of 6 to 11 carbon atoms, aryloxy, arylalkoxy or arylazo optionally substituted by chlorine or trifluoromethyl, arylthio, arylsulfinyl or arylsulfonyl, arylalkyl, straight-chain alkenyl of 2 to 6 carbon atoms or branched alkenyl of 3 to 7 carbon atoms, straight-chain alkynyl of 2 to 4 carbon atoms or branched alkynyl of 3 to 6 carbon atoms, or a fused-on benzo, benzofuran or pyridino; 3 R and R are each independently hydrogen; any one 1 of the meanings given for R ; alkyl optionally substituted by chlorine, bromine, fluorine, nitro, cyano, methoxy or ethoxy; cyeloalkyl optionally substituted by chlorine or trifluoromethyl; or aralkyl; X is oxygen or sulfur; and g 5 R is hydrogen or is OR , SR or N 7 where R5 has any one of the meanings given for R1 or is alkyl optionally substituted by chlorine, fluorine, bromine, methoxy, ethoxy, butoxy, cyclohexoxy, methylmercapto or ethylmercapto; alkenyl optionally substituted by chlorine; alkynyl optionally substituted by chlorine; cycloalkyl; cycloalkenyl; alkanonyl; or hetarylalkyl, R6 is hydrogen or has any one of the meanings given for R3 (other than an unsubstituted or substituted m-anilino radical); and fi R , independently of R , has any one of the meanings given for R3 or is hydroxyl, alkoxy, alkylthio, cyano, ZR8 cyanoalkyl or N „, XRS Q Q R and R each independently being hydrogen or alkyl or being aryl optionally substituted by any one of the substituents given for aryl in the definition of R1; or fi 7 R and R together with the adjacent nitrogen atom are a heterocyclic radical which is optionally substituted by methyl and optionally contains one or more double bonds or one or more further heteroatoms in addition to the nitrogen atan, and the -salts of these compounds, exhibit a greater herbicidal action against certain broad-leaved species of weeds and at the same time are better tolerated by crop plants than conventional substituted phenoxyalkanecarboxylic acid derivatives.

The compounds of the general formula I may be prepared, for example, by a) reacting an acrylic acid compound of the general formula _ , R2 /R3C i, v R -0- C-C, II where R , R , R and R have the.above meanings, with hydrofluoric acid, in the presence or absence of a diluent, at from -80°C to +150°C, inihe presence or absence of a catalyst, with or without subsequent sulfurizing of the compound obtained, or si 432 b) reacting a 2-fluoroalkanecarboxylic acid of the formula κφ3 , ΐ III, R -O-C-C F \h or a salt thereof, with thionyl chloride, phosgene, phosphorus pentachloride, N,N'-carbonyldiimidazole, Ν,Ν'-carbonylditriazole, N,N'—thionyldiimidazole or N, N'-thionylditriazole or a mixture of these, in the presence or absence of a diluent, and then reacting the product with a compound of the formula 10 R4H IV where R has the above meanings other than hydroxyl, in the presence or absence of a diluent, an inorganic or organic base or a reaction accelerator, with or without subsequent sulfurizing of the compound thus obtained.

The novel compounds exist in enantiomeric forms.

Their mixture, as well as mixtures in which one optical isomer has been enriched, and also the pure forms, are equally embraced by the patent claims. The pure optical isomers can, if required, be prepared from the racemate by the conventional methods of separation, for example by fractionally crystallizing diastereomeric salts with optically active bases.

R1 is, for example, unsubstituted or substituted aryl of 6 to 20 carbon atoms, especially unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted hetaryl of 5 to 7, especially of 6, ring atoms, of which 1, 2 or 3, especially 1 or 2, are heteroatoms which (if more than 1 is present) may be identical or different, and are preferably oxygen, sulfur or nitrogen, for example unsubstituted or substituted pyridyl or pyrimidinyl. 51438 3 R and R are, for example, hydrogen, straightchain unsubstituted or substituted alkyl of 1 to 10, especially 1 to 6, carbon atoms, branched unsubstituted or substituted alkyl of 3 to 8f especially 3 to car5 bon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert.-butyl, n-pentyl, 2pentyl, 3-pentyl, 4-methyl-3-pentyl, 1-chloroethyl, trifluoromethyl, trichloromethyl, difluoromethyl, nitromethyl, cyanomethyl, 2-chloroethyl, 1-chloropropyl, 210 chloropropyl, l-chloro-2-propyl, 1-fluoroethyl, 2-fluoro ethyl, l-fluoro-2-propyl, 3-bromobutyl, 1,1,1-trifluoroisopropyl, methoxyethyl, methoxyisopropyl, ethoxy-tert.butyl or methoxy-tert.-butyl, unsubstituted or substituted cycloalkyl of 3 to 7, especially 3 to 6, carbon atoms in the ring, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-chlorocyclohexyl or 2-(trifluoromethyl)-cyclohexyl, unsubstituted or substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and 1 or 2 carbon atoms in the alkyl moiety, in particular un20 substituted or substituted benzyl or α-phenylethyl, unsubstituted or substituted aryl of 6 to 20 carbon atoms, especially unsubstituted or substituted phenyl or naphthyl, an unsubstituted or substituted hetaryl of 5 to 7, especially 5 or 6, ring atoms, of which 1, 2 or 3, especially 1 or 2, are hetero-atoms, which (if more than is present) can be identical or different and are preferably oxygen, sulfur or nitrogen, for example unsubstituted or substituted pyridyl, pyrazolyl, thienyl, furyl or pyrimidinyl.

R is, for example, unbranched alkyl of 1 to 20 carbon atoms, branched alkyl of 3 to 15 carbon atoms, straight-chain or branched alkenyl or alkynyl of 3 to 15 carbon atoms, or cycloalkyl or cycloalkenyl of 3 to 10 ring carbon atoms, or alkanonyl, each of the above radicals being unsubstituted or substituted. Examples of R are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert.-butyl, cyclobutyl, n-pentyl, 2pentyl, 3-pentyl, tert.-amyl, neopentyl, 2-methyl-but-210 yl, 3-methylbutyl, 3-methyl-but-2-yl, cyclopentyl, nhexyl, 4-methyl-pent-2-yl, 2,3-dimethylbutyl, 2-methylpent-l-yl, 2-hexyl, 3-methyl-pent-2-yl, 3-methylpentyl, 4-methylpentyl, 3-methyl-pent-3-yl, 4,4-dimethylbutyl, cyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cyclo15 heptyl, 1-octyl, 2-octyl, 3-octyl, 4-octyl, 5-octyl, 5ethyl-hept-2-yl, 2,6-dimethyl-hept-4-yl, 7-ethyl-2methyl-non-4-yl, 2,4-dimethylpent-3-yl} 3-methylhept-2yl, 5-ethyl-non-2-yl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, 20 octadecyl, nonadecyl, eicosyl, 6-ethyldec-3-ylt 6-ethyloot-3-yl, 2-methylpent-2-yl, 2,3-dimethylbut-2-yl, 2methylhex-2-yl, 3-ethylpent-3-ylJ 3-"ethylhex-3-yl, 2,3dimethylpent-3-yl, 2,4-dimethylpent-2-yl, 2,2,3-trimethylbut-3-yl, 2-methylhept-2-yl, 4-methylhept-4-yl, 2,425 dimethyloct-2-yl, 1-methylcyclopent-l-yl, 1-methylcyclohex-l-yl, 1-etnyloyclohex-l-yl, chloro-tert.-butyl, 1,1dichloro-2-methylprop-2-yl, 1,3-dichloro-2-methylprop-2yl, 1-cyclohexyl-eth-l-yl, 2-chloroethyl, 2-chloropropyl, 3-chloropropyl, l-chloroprop-2-yl, 2-chlorobutyl, 251432 chloro-2-methylprop-3-yl, 2-fluorocthyl, 2-fluoropropyl, 3- fluoropropyl, l-fluoroprop-2-yl, 2-fluorobutyl, 2fluoro-2-methylprop-3-yl, 2-bromoethyl, 3-bromopropyl, 4- chlorobutyl, 2-chlorocyclohexyl, 1,1,1-trifluoroiso5 propyl, hexafluoro-2-methyl-isopropyl, hexafluoroisopropyl, hexachloroisopropyl, 1,2-dibromoallyl, 2,2,2trifluoroethyl, l-chloro-but-2-yn-4-yl, 3-chloro-but-lyn-4-yl, l-chloro-but-2-en-4-yl, 2,2,2-trichloroethyl, 1 chloropent-2-yn-4-yl, 2,2,2-tribromoethyl, 3,4,4-tri10 chloro-but-3-en-2-yl, l-bromoprop-2-yl, 1,3-dibromoprop-2-yl, 3-chlorobut-l-en-4-yl, allyl,’ propargyl, crotyl, but-2-yn-l-yl, methallyl, but-l-en-3-yl, hut-1yn-3-yl but-l-en-4-yl, but-l-yn-4-yl, 2-methylbut-l-en3-yl, 2-methylbut-2-en-l-yl, 2-methyl-but-2-en-4-yl, 315 methyl-but-l-en-3-yl, 3-methyl-but-l-yn-3-yl, 2-methylbut-l-en-4-yl, 2-ethylhex-2-en-l-yl, hex-5-en-l-yl undec-10-en-l-yl, 1-ethynylcyclohexyl, methoxyethyl, ethoxyethyl, 3-methoxypropyl, methoxyisopropyl, 3-methoxybutyl, l-methoxy-but-2-yl, ethoxy-tert.-butyl, methoxy-tert.-butyl, cyclohexyloxy-tert.-butyl, 2methoxybutyl, 4-methoxybutyl, β-methylmercaptoethyl, βethylmercaptoethyl, 3-methylmercaptopropyl, 1-methylmercaptobut-2-yl, methylmercapto-tert.-butyl, 2-methylmercaptobutyl, 4-methylmercaptobutyl, 2-n-butoxyethyl, 2-ethoxypropyl, 3-ethoxyprop-2-yl, 2-methyl-butan-3-on2-yl, 2-methyl-p3itan-4-on-2-yl, 3-butanon-l-yl, 3-butanon-2-yl 2-propanon-l-yl 2-pentanon-l-yl and N,Nς dimethylaminoethyl. R can also be unsubstituted or substituted aryl, aralkyl, hetaryl or hetaralkyl of 6 to 12 carbon atoms in the aryl or hetaryl moiety and 1 to 3 carbon atoms in the alkyl moiety, for example unsubstituted or substituted phenyl or naphthyl or unsubstituted or substituted hetaryl of 5 or 6 ring atoms of which 1 2 or 3, especially 1 or 2, are heteroatoms which, (if more than 1 is present, can be identical or different and are preferably oxygen, nitrogen or sulfur, for example pyridyl, pyrazolyl or pyrimidinyl.

Preferred substituents of the aryl or hetaryl radical include halogen, especially fluorine, chlorine or bromine, nitro, straight-chain alkyl of 1 to 14 carbon atoms, branched alkyl of 3 to 14 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, alkoxy or alkylthio of 1 to 5 carbon atoms, haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl of up to 4 carbon atoms and up to 9 halogen atoms (especially fluorine or chlorine), formyl, cyano or thiocyanato, alkoxycarbonyl, dialkylketo, alkylcarbonyl, alkylcarbamyl, dialkylcarbamyl, acylamino or alkylaminosulfonyl of 2 to 10 carbon atoms, eg, methoxy20 carbonyl, acetonyl, propionyl, Ν,Ν-dimethylcarbamyl or butyrylamino, alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, eg. ethoxypropyl or methylmercaptomethyl, unsubstituted or substituted phenyl or phenylcarbonyl of 6 or 7 to 11 carbon atoms, unsubstituted or sub25 stituted, especially 4-substituted, aryloxy, arylalkoxy or arylazo, eg, 4-(4’-chlorophenoxy), 4-(2’,4’-dichlorophenoxy), 4-(4'-trifluoromethylphenoxy), 4-(4’-chlorophenylazo) or 4-(3’-fluorophenylazo), unsubstituted or 5143« ίο substituted arylthio, arylsulfinyl or arylsulfonyl, unsubstituted or substituted aralkyl, especially unsubstituted or substituted benzyl, straight-chain alkenyl of 2 to 6 carbon atoms or branched alkenyl of 3 to 7 carbon atoms, straight-chain alkynyl of 2 to 4 carbon atoms or branched alkynyl of 3 to 6 carbon atoms, or a fused-on ring, especially an aromatic or heterocyclic fused-on ring, eg. fused-on unsubstituted or substituted benzo benzofuran or pyridino. fi 7 10 R and R' can, together with the adjacent nitrogen, be an unsubstituted or substituted heterocyclic radical, for example a 3-membered to 7-membered heterocyclic radical which may or may not contain one or more double bonds and additional hetero-atoms such as nitro9 gen, oxygen or sulfur, eg. pyrrolidinyl, 4-methylpiperazinyl, imidazolyl, 1,2,4-triazolyl, piperidinyl or 2,6-dimethylmorpholinyl.

Examples of suitable salts are the alkali metal (Na or K) or alkaline earth metal (Mg or Ca) salts of 20 the carboxylic acids.

The reaction is advantageously carried out at from -80 to +120°C, preferably from -75 to +80°C, especially from -70 to 30°C under atmospheric or superatmospheric pressure continuously or batchwise. Advantageously, a solvent which is inert under the reaction conditions is S1 9 9 9 9 9 tetrachloroethane, amyl chloride, dichloropropane, methylene chloride, dichlorobutane, isopropyl bromide, chloroform, ethyl iodide, propyl iodide, carbon tetrachloride 1 1 1-trichloroethane 1 1 2-trichloroethane 9 9 9 9 9 9 10 trichloroethylene, pentachloroethane, 1,2-dichloroethane, 1,1-dichloroethane, n-propyl chloride, 1,2-cis-dichloroethylene, n-butyl chloride, 2-, 3- and iso-butyl chloride, chlorobenzene o- m- and p-dichlorobenzene o- m- and p-chlorotoluene and 1 2 4-trichlorobenzene ketones eg. methyl ethyl ketone, acetone, diisopropyl ketone, diethyl ketone, methyl isobutyl ketone, mesityl oxide, acetophenone, cyclohexanone, ethyl isoamyl ketone, diisobutyl ketone, methylcyclohexanone and dimethylcyclohexanone, esters, eg. methyl acetate, n-propyl acetate, 20 methyl propionate, butyl acetate, ethyl formate, methyl phthalate, methyl benzoate, ethyl acetate and phenyl acetate; nitriles, eg. acetonitrile, butyronitrile, isobutyronitrile, benzonitrile and m-ohlorobenzonitrile, sulfoxides, eg. dimethylsulfoxide and diethylsulfoxide, sulfones, eg. dimethylsulfone, diethylsulfone, methylethylsulfone and tetramethylene sulfone, aliphatic and cycloaliphatic hydrocarbons, eg. heptane, a-pinene, pinane, nonane, gasoline fractions boiling within the range of from 70 to 190°C, cyclohexane, methylcyclohexane, decalin petroleum ether hexane naphtha 2 2 4-trimethylpentane, 2,2,3-trimethylpentane, 2(3(3-trimethylpentane and octane, Ν,Ν-disubstituted acid amides, eg. dimethylformamide and dimethylacetamide, and mixtures of the above. Advantageously, the amount of solvent used is from 100 to 10,000 per cent by weight, preferably from 500 to 2,000 per cent by weight, based on starting material.

The reaction can be carried out in the presence of an accelerator as the catalyst, advantageously in an amount of from 0.001 to 2, preferably from 0.001 to 0.1, equivalent per mole of starting material II.

Suitable reaction accelerators include active charcoal, boron trifluoride, aluminum halides and antimony halides such as chlorides or bromides iron chloride 9 9 zinc chloride aluminum oxide and titanium tantalum 9 9 ' niobium, rhenium or molybdenum halides, eg. chlorides, bromides and oxychlorides.

In general, from 0.8 to 20, preferably from 1 to 20 15, moles of hydrofluoric acid are used per mole of starting material II. If, however, the hydrofluoric acid and/or the catalyst is to be used as the solvent, the stated molar ratios can be substantially exceeded; in that case it is advantageous to use from 10 to 100, especially from 10 to 30, moles of hydrogen fluoride per mole of starting material II, and/or from 0.001 to 2 especially from 0.001 to 0.1, equivalent of accelerator per mole of starting material II.

The reaction can be carried out as follows: 51433 A mixture of the starting material and hydrogen fluoride, with or without solvent, is kept at the reaction temperature for from 0.1 to 60 hours. The end product I is isolated from the reaction mixture in a conventional manner, for example by filtration and fractional distillation. It is however also possible to pour the reaction mixture onto ice and separate off the organic phase or extract it with a water-immiscible organic solvent.

In a preferred embodiment of the process according to the invention, the starting material II, in particular a solution thereof in an inert solvent is added f slowly to anhydrous hydrofluoric acid which is at from -80 to -40 °C and the reaction is then carried out for from 10 minutes to 15 hours, especially from 10 minutes to.5 hours. The sequence of addition of the reactants can also be inverted by introducing gaseous hydrogen fluoride into the other reactant.

The compounds of the formula I exhibit selective herbicidal activity. They are therefore useful as crop protection agents for the control of harmful plants in agricultural crops.

EXAMPLE 1 parts of anhydrous hydrofluoric acid are added to a solution of 17 parts by weight of methyl 2(4'-fluorophenoxy)-acrylate in 100 parts of carbon tetrachloride in a flask made of fluorinated polyethylene, whilst stirring and cooling to -65°C. The mixture is then brought to room temperature and the solvent and S1433 unconsumed hydrofluoric acid are distilled off through a condenser, under reduced pressure.

Distillation of the residue gives 13 parts (70% of theory) of methyl 2-fluoro-2-(4'-fluorophenoxy)5 propionate, of boiling point 56°C/O.O5 mm Hg.

EXAMPLE 2 parts of anhydrous hydrofluoric acid are added to a solution of 29 parts of methyl 2-(21,4'-dichlorophenoxy)-acrylate in 100 parts of petroleum ether in a flask, whilst stirring and cooling to -78°C. The reaction mixture is allowed to come to room temperature and the solvent and excess hydrogen fluoride are distilled off under slightly reduced pressure. The residue is dissolved in petroleum ether, sodium fluoride is added and the mixture is filtered.

Distillation of the filtrate gives 24 parts (77% of theory) of methyl 2-(21,4'-dichlorophenoxy)-2fluoro-propionate, of boiling point 90°C/0.1 mm Hg.

EXAMPLE 3 89 parts of 2-(2’,4'-dichlorophenoxy)-acrylic acid are dissolved in 100 parts of methylene chloride in a flask, and 80 parts of hydrogen fluoride are added, whilst stirring and cooling to -65°C. The mixture is brought to room temperature and excess hydrogen fluoride is distilled off. The crude product is stirred with n-hexane and filtered off. Yield: 86 parts (89% of theory) of 2-(21,4'-dichlorophenoxy)-2-fluoropropionic acid, of melting point 88-90°C. 51-13 2 IS ΕΧΛΜΙΊ,Ε 4 parts of anhydrous hydrofluoric acid are added to 14 parts of 2-(21,4'-dichlorophenoxy)-acrylic acid at -65°C in a stirred flask the mixture is 9 brought to room temperature whilst stirring and the excess hydrogen fluoride is then distilled off. The product is recrystallized from n-hexane. Yield: parts (59% of theory) of 2—(2*,4'-dichlorophenoxy)-2fluoropropionic acid, of melting point 88-90°C.

The preparation process a is further illustrated by the Examples in Table I. - ο ρ to ΰ ο t! · C 3 Ρ Ρ ωτ5+- c ο w t- \ο ιη t— Η cn un r- c- ρ·£ Ρρ Ρ u u L, al S ο ο ο ίΛ UN CM Ο UN m cm Ο ΙΑ CM Κ\ EXAMPLE 12 8.9 parts of thionyl chloride arc added dropwise, at 10-20°C, to a solution of 20.4 parts of imidazole in 150 parts of tetrahydrofuran. The mixture is stirred for a further 30 minutes at room temperature and .is then filtered, and 19 parts of 2-(21,4'-dichlorophenoxy)-2fluoropropionio acid are added to the filtrate. This mixture is stirred for 2 hours at room temperature, after which 5.1 parts of propane-2-thiol are added and stirring lo is continued for 6 hours at room temperature. After evaporating down the reaction mixture, the residue is taken up in methylene chloride, the solution is washed twice with water, the organic phase is dried with magnesium sulfate and the solvent is stripped off, 21 parts (90% of theory) of ' isopropyl 2-(2',4’dichlorophenoxy)-2-fluorothiopropionate are obtained; n22 = 1.5272.

The following are examples of other herbicidally active compounds of the general formula.

S1433 o o U_i 0.

P, E cn Ex. no O O'.

I co νυ cm cc in in MD .=r li O CM Q C CM Q C CM ΚΛ ·=Γ CM CM CM in CM o o <0 t*— 00 o\ O CM C\J CM CM rH cm rn κά k\ m si® kX ex έ -=r X (Π rH Ο ΙΑ 'Ό ΚΛ ΚΛ ΚΛ c— οο σ\ ο η ίΛ (Λ if -=τ CM ΓΑ -=Τ ΙΑ -ζτ «=τ -=Τ Ex. no ai-ia Ex. no c— cq σ\ o IA in in UQ KO CM KO m KO xr in ko \O so KO c— KO co KO Ex. no 51132 in X CM ϋ CO σ\ M3 σ\ x c\ -r ϋ X X K* . Ο ϋ X +> ο o V X P I CQ s s fc s o bCM K\ b- bσ\ X «sr o Φ «Ρ X z in b* M3 b- b- rH CM X Q <**> in m X o X' X cm 1 1 o o > •H X 5 1 Y z z CQ CQ b- GO r— b0\ CM 51433 II OS OCH Q Ex. no in cn co o\ σ\ o σ\ O CM m o O o rH ri ri o r· 5143 Ex. no ΗΟΟ ι> II II k Γ xj toST 5143 xj c.

E =r x x XJ C.

E =r X X GJ CC GJ X Ex. no O rd O tr\ ό GJ GJ The compounds are appLIed by spray liii-. or .lu:-.!lu. ι bo pi.mt r. or the soil with them.

The novel active ingredients can be converted into the conventional formulations, e.g. solutions, emulsions, suspension;;, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agents are being used; it should, however, ensure a fine and uniform distribution of the active ingredient. The formulations are prepared in the conventional manner, for example by diluting the active ingredient with solvent and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without organic auxiliary solvents. Suitable auxiliaries are, essentially, solvents, for example aromatics, e.g., xylene and benzene, chloroaromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines e.g., ethanolamine, dimethylformamide, and water; solid carriers, for example natural rock powders, e.g., kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.

The herbicidal agents in general contain from 0.1 to 95% by weight of active Ingredient, preferably from 5 to 90%.

The agents, and the ready-to-use preparations obtained therefrom, e.g., solutions, emulsions, suspensions, powders, dusts, paste.; or crannies, are applied In conventional manner, e.g. by spraying, atomizing, dusting, broadcasting or watering.

Examples of such formulations are given below, EXAMPLE I parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-v-pyrrolIdone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE II parts by weight of compound 2 is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE III parts by weight of compound 2 is dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE IV parts by weight of compound 3 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280°C, and 10 parts by weight of the a.lduet el' 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE V parts by weight of compound 1 Is well mixed with 5 3 parts by weight of the sodium salt of diisobutylnaphthalene-.t-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill.

EXAMPLE VI parts by weight of compound 1 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5% by weight of the active ingredient.

EXAMPLE VII parts by weight of compound 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE VIII parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable, aqueous dispersion is obtained. 31432 EXAMPLE IX pants ol' compound 1 Is Intimately mixed with 1part:: of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The influence of the novel fluoroalkanecarboxylic acid compounds on the growth of unwanted and crop plants is demonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume 3 of 300 cm , and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species.

In the preemergence treatment, the active ingredients were immediately applied to the surface of the soil as a suspension or emulsion in water by spraying through finely distributing nozzles. The amount of active ingredient applied in this treatment was equivalent to 3-0 kg/ha.

After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical agents. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals.

For the postemergence treatment, the plansts were first grown in the vessels to a height of from 5 to 20 cm, depending on growth form, before being treated. For this treatment, either plants which had been sown directly In the pots and had grown there were selected, or plants which had been frown separately as seedling;', and transplanted to the experiment vessels a few days before treatment. The amount of active ingredient applied in this treat5 ment was in some cases also equivalent to 3-0 kg/ha; other tests were run with 1.0 and 2.0 kg/ha of active ingredient.

The comparative agents were the dimethylamlne salt of 2,4-dichlorophenoxy-^-propionic acid (A), applied at 2.0 kg/ha (calculated as acid), and the dimethylamlne salt of 2-methyl-4-chloro10 phenoxy-ot-propionic acid (B), applied at 1.0 kg/ha (calculated as acid).

No cover was placed on the vessels in the postemergence treatment. The pots were set up in the greenhouse - species from wanner areas at from 20° to 30°C, and species from moderate climates at 15° to 25°C.

The experiments were run for from 3 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, denoting no damage or normal emergence, and 100 denoting nonemer20 gence or complete destruction of at least the visible plant parts.

The results obtained show that the compounds have a remarkable action on preemergence application. On postemergence application (preferred), the herbicidal effectiveness is similar; in the case of some unwanted plants, the action is better than the prior art comparative agents. What is particularly worth mentioning is the better tolerance of the new compounds by crop plants.

If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the ar./enl.s are sprayed from suitable equipment In such a mniinet* that tin; leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

In view of the good tolerance of the active ingredients and the many application methods possible, the agents according to the invention may be used in a large range of crops for removing unwanted plants.

Application rates may vary from 0.1 to 15 kg/ha and more.

The following crop plants may be mentioned by way of example: Botanical name Common name Allium cepa onions Ananas eomosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var. napus rape Brasslca napus var. napobrasslca Brassica napus var. rapa turnips Brassica rapa var. sllvestrls Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon 1emons Citrus maxima grapefruits Citrus reticulata Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumls sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Daucus carota carrots Elais guineensis oil palms Pragaria vesca strawberries Botanical name Common name Glycine max soybeans Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) cotton Hellanthus annuus sunflowers Hellanthus tuberosus Hevea brasiliensls rubber plants Hordeum vulgare barley Humulus lupulus hops Ipoinoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens cullnaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medlcago sativa alfalfa (lucerne) Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum (N. rustica) tobacco 01ea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo mungbeans Botanical name Common name Phaseolus vulgaris snapbeans, green bean.··., dry bean;: Pennisetum glaucum Petroselinum crispum spp. tuberosum parsley Picea abies Norway spruce Ables alba fir trees Pinus spp. pine trees Pisum sativum English peas 10 Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus perslca peach trees Pyrus communis pear trees 15 Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane Secale cereale rye 20 Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum doehna Splnaeia oleracea spinach 25 Theobroma cacao cacao plants Botanical name Common name Trifolium pratense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize To increase the spectrum of action and to achieve synergistic effects, the novel fluoroalkaneearboxylic acid compounds may be mixed among themselves or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl-caramates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, etc. A number of active ingredients which, when combined with the new compounds, give mixtures useful for widely varying applications are given below by way of example: methyl oi -naphthoxyac etat e 2-(2-methylphenoxy)-propionic acid amides) 2-(4-chlorophenoxy)-propionic acid amides) 2-(2,4-dichlorophenoxy)-propionic acid amides) (salts, esters, (salts, esters, (salts, esters 2-(2,4,5-trichlorophenoxy)-propionic acid amides) (salts, esters , 2-(2-methyl-4-chlorophenoxy)-propionic acid amides) (salts, esters, 5 4-(2,4-dlchlorophenoxy)-butyrlc acid amides) (salts, esters, 4-(2-methyl-4-chlorophenoxy)-butyric acid amides) eyclohexyl-3-(2,4-dichlorophenoxy)-acrylate (salts, esters, 10 9-hydroxyfluorenecarboxyllc acid-(9) (salts, esters) 2,3,6-trichlorophenylacetic acid (salts, esters) 4- ehloro-2-oxobenzothiazolin~3-yl-acetic acid (salts, esters) gibelleric acid (salts) disodium methylarsonate 15 monosodium salt of methylarsonic acid N-phosphonomethyl-glyeine (salts) N, N-bis-(phosphonomethyl)-glycine (salts) 2-chloroethyl 2-chloroethanephosphonate ammonium-ethyl-carbamoyl-phosphonate di-n-butyl-l-n-butylamino-cyclohexyl-phosphonate trithiobutylphosphite O, 0-dilsopropyl-5-(2-benzosulfonylaminoethyl)-phosphorodithioate 2,3-dihydro-5,6-dimethyl-l,4-dithiin-l,1,4,4-tetraoxide - tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)"l,3,4-oxa25 diazolone-(2) 4,5-dichloro-2-trifluoromethylbenzimidazole (salts) 1,2,3,6-tet rahydropyridazine-3,6-dione (salts) succinic acid mono-N-dimethylhydrazide (salts) (2-chloroethyl)-trimethylammonium chloride (2-methyl-4-phenylsulfonyl)-trlfluoromethanesulfone anilide l,l-dimethyl-4,6-dlisopropyl-5-indanyl ethyl ketone sodium chlorate ammonium thiocyanate calcium cyanamide, -amino-4-chloro-2-phenyl-3(2H)-pyridazinone -amino-4-b romo-2-phenyl-3(2H)-pyridazinone -amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone -amlno-4-bromo-2-cyclohexyl-3(2H)-pyridazinone -methylamino-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone -methylamino-4-chloro-2-(3- , ,β,β-tetrafluoroethoxyphenyl)15 -3(2H)-pyridazinone -dlmethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone 4.5- dimethoxy-2-pheny1-3(2H)-pyridazinone 4.5- dlmethoxy-2-cyclohexyl-3(2H)-pyridazinone 4.5- dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone -methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone 5-amino-4-b romo-2(3-methylphenyl)-3(2H)-pyr idaz inone 3-(l-methylethyl)-1Η-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts 3-(1 -methylethyl )-8-cbloro-lH-2,l,3-benzothiadiazin-4(3H)-one-2,2-dioxlde and salts 3-(1-methylethyl)-8-fluoro-lH-2,l,3-benzothiadlazin-4(3H)-one-2,2-dloxide and salts 3-(1-methylethyl)-8-methyl-lH-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxlde and salts l-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadlazin-4(3H)-one-2,2-dioxlde l-methoxymethyl-8-ohloiO-3-(l-methylethyl)-2,1,3-benzothia10 diazin-4(3H)-one-2,2-dioxide l-methoxymethyl-8-fluoro-3-(l-methylethyl)-2,l,3-benzothiadiazin-4(3H)-one-2,2-dioxide l-cyano-8-chloro-3-(1-methylethyl)-2,l,3-benzothladiazin-4(3H)-one-2,2-dioxide l-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide l-eyano-8-methyl-3-(l-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide l-cyano-3-d-methylethyl)-2,l,3-benzothiadiazln-4(3H)-one-2,220 -dioxide l-azidomethyl-3-(l-methylethyl)-2,l,3-benzothiadiazin-4(3H)-one-2,2-dioxide 3-(1-methylethyl)-ΙΗ-pyridino-[3,2-e]-2,1,3-thiadiazin-(4)-one-2,2-dioxlde ί;> N-(l-e thy lpropy 1)-2,6-d initro-3,!l-dlinethylaniline N-d-mi’tb.vlrt-hyl 1-N-et hyl-2 , 6-il i nl V.t’o-l| -1, r l fluor.mii't hyl anil in·· N-11-propyl -Μ-β-elil nrorl.liy 1-2,6-d tn 1I. ro-4-l, r IT1 uoromnthy l.-1 ii 1 I i in· N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethylaniline N-b is-(n-propyl )-2, e-dinitro-S-amino-it-trif luoromethyl anil ine N-bis-(n-propyl)-2,6-dinltro-4-methylanillne N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline N-bis-( n-propyl )-2,6-dinitro-it-aminosulfonylaniline bis-(B-chloroethyl)-2,6-dinitro-4-methylaniline N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline 3,4-dichlorobenzyl N-methylcarbamate 2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate isopropyl N-phenylcarbamate 3- methoxyprop-2-yl N-3-fluorophenylcarbamate isopropyl N-3-chlorophenylcarbamate but-l-yn-3-yl N-3-chlorophenylcarbamate 4- chlorobut-2-yn_l-yl N-3-chlorophenylcarbamate methyl N-3,4-dlchlorophenylcarbamate methyl N-(4-aminobenzenesulfonyl)-carbamate 0-(N-phenylcarbamoyl)-propanone oxime N-ethyl-2-(phenylearbamoyl)-oxypropionic acid amide 3'-N-isopropylcarbamoyloxypropionanilide 5143« ethyl-N-(3-(N*-phenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N '-methyl-N '-phenylcarbamoyloxy)-pheny3.)-carbamate isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamo,yloxy)-phonyl)-earbamate methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3- (N '-If-fluorophenylcarbamoyloxy )-phenyl )-carbamate methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate ethyl-N-C3-N'-O-chloro-Jf-f luo rophenylearbamoxyloxy)-phenyl ΙΙΟ -carbamate ethyl-N-C3-N'-(3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate methyl-N-[3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate methyl N-3-(4 '-fluorophenoxycarbonylamino)-phenyl carbamate ethyl N-3-(2'-methylphenoxyearbonylamlno)-phenylearbamate methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiolcarbamate methyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate p-chlorobenzyl N,N-diethylthiolcarbamate ethyl N,N-di-n-propylthiolearbamate n-propyl N,N-di-n-propylthiolcarbamate 2.3- dichloroallyl N,N-dlisopropylthiolcarbamate 2.3.3- trichloroallyl Ν,Ν-diisopropylthiolcarbamate 3-ini' ι hyl-5-tsoxazolylmothyl N ,N_d lisopropylthlo I carbamate 1 1-11.y I -1)- I ;·..x;i;'.o I y I mi >1.1 i.y 1 M, N-il I 1 r.opropy 1 Lb I ο I rn |·|ι;ιιιι.Ί t.i· l-l i.y I N, N-i| I -sec .-butyl llilo I carbamate benzyl N,N-d1-sec.-butylthiolearbamate ethyl N-ethyl-N-cyclohexylthiolearbamate ethyl N-ethyl-N-bicyclo-[2.2.l]-heptylthiolearbamate S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-l-carbothiolate 3-(2,3,3-triehloroallyl)-(2,2,4-t rimethylazetidine)-l-carbothiolate S-ethylhexahydro-l-H-azepine-l-carbothiolate S-benzyl-(3-methylhexahydro-l-H-azepine-l)-earbothiolate S-benzyl-(2,3-dimethylhexahydro-l-H-azepine-l)-carbothiolate S-ethyl-(3-methylhexahydro-l-H-azepine-l)-carbothiolate n-propyl N-ethyl-N-n-butylthiolearbamate 2-chl oroallyl N,N-dimethyldithiocarbamate N-methyldithiocarbamic acid, sodium salt trichloroacetic acid, sodium salt ιΧ,,,^-dichloropropionie acid, sodium salt cZx-dichlorobutyric acid, sodium salt ίΖχ-β,β-tetrafluoropropionic acid, sodium salt oC-methyl-AijB-dichloropropionic acid, sodium salt methyl / -chloro-β- (4-chlorophenyl )-propionate methyl/ ,β-dichloro-B-phenylpropionate benzamido oxyacetic acid 2.3.5- triiodobenzoic acid (salts, esters, amides) 2.3.6- trichlorobenzoic acid (salts, esters, amides) 514 3 2 2, 3, η, 6-t.et. radii nrobi'tisu 1 e a« 1 d 2-niethoxy-3,6-dlchlorot)enxo ic acid 2- »iefch(»x.y-3,*>, 6-l.r I chlorebenzoic acid 3- amino-2,5,6-triehloroberizoic acid (i’.a 1 1.::, e:;I err., am i i1<·;:) (salts, eaters, amide::) (::a 1 I. ter::, amide:'·) (salt.:;, esters, amides) 0,S-dimethyltetrachlorothioterephthalate dimethyl-2,3,5,6-tet rachloroterephthalate disodium 3,6-endoxohexahydrophthalate 4-amino-3,5,6-trichloropicolinic acid (salts) ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate isobutyl 2-[4-(4'-chiorophenoxy)-phenoxy)-propionate methyl 2-(4-(21,4'-dlchlorophenoxy)-phenoxy]-propionate methyl 2-[4-(4'-trlfluoromethylphenoxy)-phenoxy]-propionate 2-(4-(2'-chloro-4'-trifluorophenoxy)-phenoxy)-propionic acid, sodium salt 2-(4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt ethyl 2-(N-benzoyl-3,4-dichlorophenylamino)-propionate methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-proplonate Isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate 2-chloro-4-ethylamino-6-isopropylamlno-l,3,5-t riazine 2-ehloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine 2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-l,3,5-triazine 2-chloro-4-ethylamino-6-butyn-l-yl-2-amino-l,3,5-triazine 2-chloro-4,6-bisethylamino-1,3,5-t riazine 514 3 2 2-chloro-4,6-bisisopropylamino-1,3,5-triazine 2-chloro-4-isopropyl amino-6-eyclopropylamino-1,3,5-triazine 2-azido-4-methylami no-6-isopropylamlno-1,3,5-tri;tzino 2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine 2-methylthio-4,6-b isethylamino-1,3,5-t riazine 2-methylthio-4,6-bisisopropylamino-l,3,5-triazine 2-methoxy-4-ethylamino-6-isopropylamino-l,3j5-triazine 2- methoxy-4,6-bisethylamino-1,3,5-triazine 2-methoxy-4,6-b is isopropylamino-1,3,5-t riazine 4-amino-6-tert .butyl-3-methylthio-4,5-dihydro-l,2,4-triazin-5-one 4-amino-6-phenyl-3-methyl-4,5-dihydro-l,2,4-triazin-5-one 4-isobutylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro-l,2,4-trlazin-5-one l-methyl-3-cyclohexyl-6-dimethylamino-1,3a5-triazin-2,4-dione 3- tert.butyl-5-ehloro-6-methyluracil 3-tert.butyl-5-bromo-6-methyluracil 3-isopropyl-5-bromo-6-methyluracil 3-sec.butyl-5-bromo-6-methyluracil 3-(2-tetrahydropyranyl)-5-ehloro-6-methyluracil 3-(2-tetrahyd ropyranyl)-5,6-trimethyleneurac il 3-cyclohexyl-5,6-trimethyleneuracil 2-metliyl-4-(3 '-tririuoroinethyl phenyl )-tetrahydro-l ,2,4-oxaι| 1 a·/, i in·- 1, 'ι-il I uni* 2- rn thy 1.-4-(4 '-Γίιιοί'ΐ'phenyl )-t(’trahyiiro-1 ,2,4-oxad las.I tn — 1 ,*>-diotie 3- amlno-l,2,4-t riazole l-allyloxy-l-(4-bromophenyl)-2-[l1,2' ,4'-triazolyl-(l')]-ethane (salts) 1- (4-chlorophenoxy)-3,3-dlinethyl-l-(lH-l,2,3-triazol-l-yl )-butan-2-one Ν,Ν-diallylchloroacetamide N-lsopropyl-2-chloroacetanllide N-(l-methylpropyn-2-yl)-2-chloroacetanilide 2- methyl-6-ethyl-N-propa rgyl-2-chloroac etanillde 2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanlllde 2-methyl-6-ethyl-N-(2-methoxy-l-methylethyl)-2-chloroacetanilide 2-methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanlllde 2-methyl-6-ethyl-N-(4-methoxypyrazol-l-yl-methyl)-2-chloro-acetanilide 2-methyl-6-ethyl-N-(pyrazol-l-yl-methyl)-2-chloroacetanilide 2.6- dlmethyl-N-(pyrazol-l-yl-methyl)-2-chloroacetanilide 2.6- dimetbyl-N-(4-methylpyrazol-l-yl-methyl)-2-chloro-acetanillde 2.6- dimethyl-N-(1,2,4-triazol-l-yl-methyl)-2-chloroacetanilide 2.6- dimethyl-N-(3,5-dimethylpyrazol-l-yl-methyl)-2-chloroacetanilide 2.6- dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanlllde 2.6- dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide 2.6- ιI imethyl-N-i;;obutoxyinetliyl-2-ciiloroaeetanilide 2.6- d i ethyl -N-methoxyiiiethyl-P-chloroac.otantl ide 2, 6-d i i-tliy L-N-n-butuxymethyl-2-r iiloroacetanILido 2.6- d lathyi-N-ethoxyearbonyliiiotliyl-2-chloroaeetaii 11 Ide 2.3.6- trimethyl-N-(pyrazol-l-yl-methyl)-2-chloroacetanilide 2,3-dimethyl-N-isopropyl-2-chloroacetanilide 2.6- diethyl-N-(propoxyethyl)-2-chloroacetanilide 2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide 2-( -naphthoxy)-N,N-diethylpropionamide 2,2-diphenyl-N,N-dimethylacetamide -(3,4,5-trib romopyrazol-l-yl)-N,N-dimethylpropionamide N-(l,1-dimethylpropynyl)-3,5-dichlorobenzamide N-l-naphthylphthalamic acid propionic acid 3,4-dichloroanilide cyclopropanecarboxylic acid 3,4-dichloroanilide methacrylic acid 3,4-dichloroanilide 2-methylpentanecarboxyllc acid 3,4-dichloroanilide -acetamido-2,4-dimethyltrifluoromethanesulfone anilide -acetamido-4-methyltrifluoromethanesulfone anilide 2-propionylamino-4-methyl-5-chlorothiazole 0-(methylsulfonyl)-glycolic acid N-ethoxymethyl-2,6-dimethylanil ide 0-(methylamlnosulfonyl)-glycolic acid N-isopropylanilide 0-(isopropylaminosulfonyl)-glycolic acid N-but-l-yn-3-yl-anilide 0-(methylaminosulfonyl)-glycolie acid hexamethyl eneamide 2.6- dichlorothiobenzamide 2.6- dichlorobenzonltrile 514 3 2 3.5- dibromo-4-hydroxybenzonltrile (salts) 3.5- diiodo-4-hyd roxybenzonitrile (salts) 3.5- dibromo-4-hydroxy-0-2,4-dlnitrophenylbenzaldoxime (salts) 3.5- dibromo-4-hydroxy-0-2-cyano-4-nitrophenylbenzaldoxime 5 (salts) pentachlorophenol, sodium salt 2.4- dichlorophenyl-4'-nitrophenyl ether 2,4,6-trichlorophenyl-4’-nitrophenyl ether 2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether 2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether 2,4'-dinitro-4-trifluoromethyl-diphenyl ether 2.4- dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether 2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether (salts) 2.4- dichlorophenyl-3'-methoxycarbonyl-4'-nitro-phenyl ether 2-(3,4-dichlorophenyl)-4-methyl-l,2,4-oxadiazolidine-3,5-dlone 2-(3-tert.butylearbamoyloxyphenyl)-4-methyl-l,2,4-oxadiazolidine-3,5-dione 2-(3-isopropylcarbamoyloxyphenyl)-4-methyl-l,2,4-oxadiazolidine-3,5-dione 2-phenyl-3,1-benzoxazinone-(4) (4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-(5,4,1,02,^’0,®’111-dodeca-3,9-diene 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyldimethylamlnosulfonate 2-ethoxy-2,3-dih.ydro-3,3-diinethyl-5-benzofuranyl-(N-met;hyl-N-ncet.vl 1 - ami iior.ulfonato 3,4-d Lchloro-l ,2-berrz isoth Lazo J e N-4-chlorophenyl-allylsuccinimide 2-methyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol acetate 2-tert.butyl-4,6-dinitrophenol acetate 2-tert.butyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol acetate 2-sec.amyl-4,6-dinitrophenol (salts, esters) 1-fci ,y-dimethylbenzyl)-3-(4-methylphenyl)-urea 1-phenyl-3-(2-methyleyelohexyl)-urea l-phenyl-l-benzoyl-3,3-dimethylurea 1-(4-ehlorophenyl)-1-benzoyl-3,3-dimethylurea 1-(4-chlorophenyl)-3,3-dimethylurea 1-(4-chlorophenyl)-3-methyl-3-but-l-yn-3-yl-urea 1-(3,4-dichlorophenyl)-3,3-dimethylurea 1-(3,4-dichlorophenyl)-l-benzoyl-3,3-dimethylurea 1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea 1-(4-isopropylphenyl)-3,3-dimethylurea 1-(3-trifluoromethylphenyl)-3,3-dimethylurea 1-(3-^ ,ο/,β,β-tetrafluoroethoxyphenyl )-3,3-dimethylurea l-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea 1-(3-chl or o-4-methyl phenyl )-3,3-dimethylurea l-(3-chloro~4-inethexypheriy L )-3 > 3-d Imethylurea 1-(3,5-dichloro-4-methoxyphenyl )-3,3-d hnothyl urea 1-(4-(41 -ehlorophenoxy)-phenylJ-3,3-d hnethy L urea 1-(4-(41-methoxyphenoxy)-phenyl]-3,3-dImethylurea l-cyclooctyl-3,3-dimethylurea 1-(hexahydro-4,7-methanoindan-5-yl)-3,3-dlmethylurea 1-(1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-dimethylurea 1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea l-phenyl-3-methyl-3-methoxyurea 1-(4-chlorophenyl)-3-methyl-3-methoxyurea l_(4_bromophenyl)-3-methyl-3-methoxyurea 1-(3,4-dlehlorophenyl)-3-methyl-3-methoxyurea l-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea l-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea l-(3-chloro-4-methoxyphenyl)-3-methyl-3-niethoxyurea 1-(3-t ert.b utylphenyl)-3-methyl-3-methoxyurea 1-(2-benzthlazolyl)-1,3-dlmethylurea l-(2-benzthlazolyl)-3-methylurea 1-(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dlmethylurea lmldazolldln-2-one-l-carboxylic acid isobutylamide 1.2- dimethyl-3,5-diphenylpyrazolium-methylsulfate 1.2.4- trimethyl-3,5-diphenylpyrazolium-methylsulfate 1.2- dimethyl-4-bromo-3,5-dlphenylpyrazoliunMiiethyl sulfate 1.3- d imethyl-4-( 3,4-dichlorobenzoyl )-5-( 4-methyl phenyl sulf onyloxy)-pyrazole 2.3.5- trichloropyridlnol-(4) 514 3 2 1-πι^61ι.γ1-3-ρ6οη,γ1-5-(3 '-trifluoromethylphenyl)-pyridone-(4) 1- methyl-4-phenylpyridinium chloride 1,1-dimetnylpyridinium chloride 3-phenyl-4-hydroxy-6-chloropyridazine 1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate) 1,1'-di-(3,5-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridylium dichloride 1,1’-ethylene-2,2'-dipyridylium dibromide 3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran10 -2,4-dione 3-[l-(N-allyloxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione 2- [l-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-l,3-dione (salts) 2-[l-(N-allyloxyamino-butylidene]-5,5-dimethylcyelohexane-l,3-dione (salts) 2-(l-(N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl-cyclohexane-l,3-dione (salts) 2-chlorophenoxyacetie acid 20 4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid 2.4.5- trichlorophenoxyacetic acid 2-methyl-4-chlorophenoxyacetic acid 3.5.6- trichloro-2-pyridinyl-oxyacetic 25 acid (salts, esters, amides) (salts, esters, amides) (salts, esters, amides) (salts, esters, amides) (salts, esters, amides) (salts, esters, amides) 2-chloro-4-trifluoromethyl-3’-ethoxycarbonyl-4'-nitrophenyl ether 1-(4-b enzyloxyphenyl)-3-methyl-3-methoxyurea 514 3 2 2- [l-(2,5-ditnethylphenyl )-ethyLsul Cony I J-pyrkl I iu'-N-i>x M·1- aeet,yl-3-anilino-4-methoxyearbonyl-5-methylpyi'nzole 3- anilino-4-methoxycarbonyl-5-methylpyrazole 3-t ert. butyl amino-4-methoxycarbonyl-5-mothylpyr:T.;ole N-benzyl-N-isopropyl-trimethylacetamide methyl 2-(4-(41-chiorophenoxymethyl)-phenoxy)-propionate ethyl 2-(4-(5'-bromopyridyl-2-oxy)-phenoxy]-propionate ethyl 2-(4-(5'-iodopyridyl-2-oxy)-phenoxy]-proplonate n-butyl 2-(4-(5'-lodopyridyl-2-oxy)-phenoxy]-propionate 2- chloro-4-trifluoromethylphenyl-3'-(2-fluoroethoxy)-4'-nitrophenyl ether 2-chloro-4-trifluoromethylphenyl-3-( ethoxycarbonyl )-methyl-thio-4-nitrophenyl ether 2,4,6-trichlorophenyl-3-(ethoxyearbonyl)-methylthio-4-nitro-phenyl ether 2-(1-(N-ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-l-one (salts) 2-[1-(N-ethoxamino)-butylidene]-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-l-one (salts) ethyl 4-[4-(4'-trifluoromethyl)-phenoxy]-pentene-2-earboxylate 2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrophenyl ether 2.4- dichlorophenyl-3'-carboxy-4’-nitrophenyl ether (salts) 4.5- dimethoxy-2-(3- , ,B-trifluoro-fi-bromoethoxyphenyl)-3-(2H)-pyridazinone 2,4-dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl ether 2,3-dihydro-3,3-dimethyl-5-benzofuranyl-ethane sulfonate 51433 N- f4-rnethoxy-6-methyl-1,3, 5-triaulH-.’-yl-aiiiliiocarbonyl l-.'-clil oivbenzene sulfonamide 1-(3-chloro-4-ethoxyphenyl)-3,3-dimethylurea ethyl 2-methyl-4-chlorophenoxy-thloacetate 2-chioro-3,5-diiodo-4-acetoxy-pyridine 1-(4-[2-(4-methylphenyl)-ethoxy]-phehyl-3-methyl-3-methoxyurea.

It may also be useful to apply the novel compounds, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

In investigations into the herbicidal action on postemergence application in the greenhouse, novel compound no. 2 exhibits, at 2.0 kg/ha, a better selective herbicidal action than prior art active ingredient A.

Active ingredient no. 3 also exhibits, on postemergence application in the greenhouse at 1,0 kg/ha, a better selective herbicidal action than prior art active Ingredient B at the sitae rate (calculated as acid).

In investigations Into the herbicidal action on pre- and postemergence application in the greenhouse, novel active ingredients nos. 6, 8, 11, 22 and 56 exhibited, at 3 kg/ha, a good herbicidal action.

In further experiments on postoinergence application in the greenhouse, compound no. 27 was tolerated very well, and compound no. 25 acceptably, by the crop plant rice when they were applied at 1.0 kg/ha. At the same time, broadleaved unwanted plants wort; seriously damaged. Of decisive importance here is the fact that the compounds are excellently tolerated by a crop plant from the Gramineae family.

Claims (19)

1. general A 2-fluoroalkanecarboxylic acid compound of the formula Β 2 E 3 r^O-C-C* 5 ^ F R 5 where R 1 is aryl or hetaryl optionally substituted by halogen, nitro,straight-chain alkyl of 1 to 14 carbon atoms, branched alkyl of 3 to 14 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, alkoxy or alkylthio of 1 to 5 carbon atoms, haloalkyl, 10 haloalkoxy, haloalkylthio or haloalkylsulfonyl of up to 4 carbon atoms and up to 9 halogen atoms, formyl, cyano or thiocyanato, alkoxycarbonyl, dialkylketo, alkylcarbonyl, alkylcarbamyl, dialkylcarbamyl, acylamino or alkylaminosulfonyl of 2 to 10 carbon atoms, alkoxyalkyl or alkyl15 thioalkyl of 2 to 6 carbon atoms, phenyl or phenylcarbonyl of 6 to 11 carbon atoms, aryloxy, arylalkoxy or arylazo optionally substituted by chlorine or trifluoromethyl, arylthio, arylsulfinyl or arylsulfonyl, arylalkyl, straightchain alkenyl of 2 to 6 carbon atoms or branched alkenyl of 3 to 7 carbon atoms, straight-chain alkynyl of 2 to 4 carbon atoms or branched alkynyl of 3 to 6 carbon atoms, or a fusedon benzo, benzofuran or pyridino;

2. 3 R and R are each independently hydrogen; any one of the meanings given for R 1 ; alkyl optionally substituted by chlorine, bromine, fluorine, nitro, cyano, methoxy or ethoxy; cycloalkyl optionally substituted by chlorine or trifluoromethyl ; or aralkyl; X is oxygen or sulfur; and 4 5 5 R R is hydrogen or is OR , SR or Νζ/ R where R has any one of the meanings given for R 1 or is alkyl optionally substituted by chlorine, fluorine, bromine, 51433 methoxy, ethoxy, butoxy, cyclohexoxy, methylmercapto or ethylmercapto; alkenyl optionally substituted by chlorine; alkynyl optionally substituted by chlorine; cycloalkyl; cycloalkenyl; alkanonyl; or hetarylalkyl, 5 R 6 is hydrogen or has any one of the meanings given for c R (other than an unsubstituted or substituted m-anilino radical); and 7 fi R , independently of R , has any one of the meanings given for R 5 or is hydroxyl, alkoxy, alkylthio, cyano, cyd8 10 anoalkyl or X R 9 8 9 R and R each independently being hydrogen or alkyl or being aryl optionally substituted by any one of the substituents given for aryl in the definition of R 1 ; or fi 7 R and R together with the adjacent nitrogen atom are 15 a heterocyclic radical which is optionally substituted by methyl and optionally contains one or more double bonds or one or more further heteroatoms in addition to the nitrogen atom; or a salt of any of the above compounds, 20 2, A compound as claimed in claim 1, wherein any radical R 3 , R 2 , R 3 , R 3 , R 3 , R? , R 3 and R 3 is unsibstituted.

3. A compound as claimed in claim 1 or 2, wherein any aryl radical has 6 to 20 carbon atoms, any hetaryl radical has 5 to 7 ring carbon atoms, any alkyl radical 25 has 1 to 10 carbon atoms, any cycloalkyl or cycloalkenyl radical has 3 to 10 ring carbon atoms, any aralkyl radical has 6 to 10 carbon atoms in the aryl moiety '· and 1 or 2 carbon atoms in the •ilkyl moiety and any alkenyl or alkynyl radical has 3 to L5 carbon atoms. 1 2

4. A compound as claimed in claim 1, wherein R , R and each denote one of the individual radicals separately named herein as examples of them and X and R have the eg 7 meanings given in claim 1 where R , R and R each denote one of the individual radicals separately named herein as examples of them.

5. A compound as claimed in claim 1 and identified in any of the foregoing Examples 1 to 126.

6. 2-(2',4'-Dichlorophenoxy)-2-fluoropropionic acid.

7. Methyl 2-(2',4'-dichlorophenoxy)-2-fluoropropionate.

8. Isooctyl 2-(2',4*-dichlorophenoxy)-2-fluoropropionate.

9. Methyl 2-(3'-trifluoromethylphenoxy)-2-fluoropropionate

10. Methyl ?-(4 1 -fluorophenoxy)-2-fluoropropionate.

11. ?-(;-Mothyl-4'-chlorophenoxy)-2-fluoropropionic acid.

12. ?-(5-Chlorophenoxy)-ethyl-2-(2',4'-dichlorophenoxy)-2-fluoropropionate.

13. A process for the manufacture of a 2-fluoroalkanecarboxylic acid compound as claimed iri claim 1, wherein ari acrylic acid compound of the general formula R 2 R 3 R -O-C-C ' XI V 12 3 4 where R , R', R and R have the meanings given in claim 1, is reacted with hydrofluoric acid, in the presence or absence of a diluent, at from -80°C to +150°C, in the presence or absence of a catalyst, with or without subsequent sulfurizing of the compound obtained.

14. A process for the manufacture of a 2-fluoroalkanecarboxylic acid compound as claimed in claim 1, wherein a ‘-fluoroalkanecarboxylic acid of the formula 1 · j, OH III, or a salt thereof, where R 1 , R 2 and R 3 have the meanings given in claim 1, is reacted with thionyl chloride, phosgene, phosphorus pentachloride, N,Ν'-carbonyldiimidazole, N,N’carbonylditriazole, N,N'-thionyldiimidazole or Ν,Ν'-thionylditriazole or a mixture of two or more of these, in the presence or absence of a diluent, and the product is then reacted with a compound of the formula R^H IV, a where R has the meaning given in claim 1 excluding hydroxyl, in the presence or absence of a diluent, an inorganic or organic base or a reaction accelerator, with or without subsequent sulfurizing of the compound thus obtained.

15. A 2-fluoroalkanecarboxylic acid compound when prepared by the process as claimed in claim 13 or 14.

16. A herbicide comprising a solid or liquid carrier and a 2-fluoroalkanecarboxylic acid compound as claimed in any of claims 1 to 12 or 15.

17. A process for the manufacture of a herbicide, wherein a solid or liquid carrier is mixed with a 2-fluoroalkanecarboxylic acid compound as claimed in any of claims 1 to 1? or 15.

18. A process for combating the growth of unwanted plants, wherein the plants or the soil are treated with a 2-fluoroalkanecarboxylic acid compound as claimed in any of claims 1 to 12 or 15.

19. A process for selectively combating weeds in an agricultural crop, wherein the crop area 13 treated post60 51433 nergcnce with a 2-f1uoroalkanecarboxylic acid compound as claimed in any of claims 1 to 12 or 15.