DD200066A5 - HERBICIDE MEDIUM - 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 new herbicides can be used in agriculture as "5 * weedkillers.

Characteristics of the known technical solutions are known Phenoxyalkancarbonsäurederivate - for example, the dimethylamine salt of 2-methyl-4-chlorophenoxy-t ^ - s ~ \ 10 propionic acid (DE-AS 10 64 286) or the dimethylamine salt of 2,4-dichlorophenoxy ^ -propionic acid (DE-PS 15 42 791) to be used as herbicides.

The discovery of the herbicidal action of phenoxyalkanecarboxylic acids in 1942 made it possible to control numerous broadleaf weeds in crops of graminaceous crops such as cereals, corn or rice. Other phenoxy fatty acid derivatives with special properties were later added as individual products or as a mixing partner.

In an extensive literature chemistry, (applications, advantages and disadvantages of the known compounds of this class, including their salts and esters are explained (Wegler, R. - chemistry of pesticides, Vol 5, 1977) Despite the global.. The use of phenoxyalkanoic acids is not to be overlooked because their use poses a certain risk to the crops and is attempted to reduce this by the 30th most precise application of the active ingredients at times of certain less sensitive growth stages of crops.

23212 5 1

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"" Object of the invention .

The aim of the invention is the development of herbicidal agents with improved efficiency in weeds, but crops are not damaged. 5

Explanation of the essence of the invention

The invention has for its object to provide new chemical compounds with herbicidal activity.

It has now been found that 2-fluoroalkanecarboxylic acid compounds of the general formula

R ³

2 '

R-C-H

5 R ¹ -0-CC ^ ₁₁ ^X

_p R

wherein

R is an optionally substituted aryl or heteroaryl

aryl radical,

2 λ

R and R ^J is independently hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl,

Oxygen or sulfur and

4 R

mean, in which

Seoff or sulfur and R is a hydroxyl group or the groups OR, SR or

R is an optionally substituted alkyl, alkenyl,

Alkynyl, cycloalkyl, cycloalkenyl, alkanone, aryl, heteroaryl or heteroarylalkyl radical,

R is hydrogen or the radicals mentioned for R 1, except for an optionally substituted m-anilino radical,

7 ft ^

R 'regardless of R's for B? mentioned radicals or

a hydroxyl group or an optionally substituted alkoxy or alkylthio radical, a cyano

232125 1

- 3 - 0.2. OO5O / O34586

or cyanoalkyl group or the remainder

"8 Nc ^ Q means ^

8 9 wherein R and R ^ are independently hydrogen or

a -. 5 is an optionally substituted alkyl or aryl radical

6 and also R and R together with the adjacent one

Nitrogen atom represent an optionally substituted heterocyclic ^j cyclic radical, optionally containing one or more double bonds, or in addition to the nitrogen f ~ atom y 10 containing one or more hetero atoms, or the salts of these compounds an improved herbicidal activity against certain broad-leaved weed species and simultaneously have more favorable compatibility for crop plants than known substituted phenoxyalkanecarbon-J5 acid derivatives.

The compounds of the general formula I are prepared, for example, by reacting a) an acrylic acid compound of the general formula

20

R ² .R ³

^N c · 'o

O R ³ -OCC ^ II

^u V

wherein R, R, R ^J and R have the abovementioned meanings, if appropriate with hydrofluoric acid with or without a diluent at temperatures between -80 ° C and + 150 ⁰ C in the presence of a catalyst and the resulting compounds where appropriate or schwefelt

b) a 2-fluoroalkanoic acid of the formula

2 ^H ? R ² i, R ³

C 0 III

R-Lo-c-c

F ^X 0H

232125 V

· · · · · · · · · · · · · · ·:::: -4- 0.2.0050 / 034586

or salts thereof with thionyl chloride, phosgene, phosphoryl ^chloride , Ν, Ν'-carbonyldiimidazole, N, N'-carbonylditriazole, Ν, Ν'-thionyldiimidazole or N, N'-thionylditriazole or mixtures thereof, if appropriate in the presence of a diluent and thereafter with a compound of the formula

R ⁴ H IV

h wherein R has the meanings mentioned above other than a hydroxyl group, if appropriate in the presence of a diluent, of an inorganic or organic base or a reaction accelerator and the compound thus obtained is optionally schwefeit.

The new substances occur in enantiomeric forms. Their mixture and the optically enriched or pure forms are covered by the claims. If desired, the pure optical isomers can be prepared from the racemate by the customary separation methods, for example by fractional crystallization of diastereomeric salts with optically active bases.

R is, for example, an optionally substituted aryl radical having 6 to 20 carbon atoms, in particular optionally substituted phenyl, naphthyl; an optionally substituted heteroaryl radical having 5 to 7, in particular 6 ring atoms, of which 1 to 3, in particular 1 to 2 heteroatoms which may be identical or different and are preferably oxygen, sulfur or nitrogen, for example an optionally substituted pyridyl or pyrimidinyl radical ,

232125 1

' :. ^. - 5 - 0-2. 0050/03 ^ 586

For example, R _% and R 1 represent hydrogen, straight-chain, optionally substituted alkyl having 1 to 10, in particular 1 to 6 carbon atoms, branched, optionally substituted alkyl having 3 to 8, in particular 3 to 6 carbon atoms, for example methyl, ethyl, n-propyl iso-propyl, η-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 4-methyl-3-pentyl, 1-chloroethyl, trifluoromethyl, trichloromethyl, difluoromethyl, nitromethyl, Cyanomethyl, 2-chloroethyl, 1-chloropropyl, 2-chloropropyl, 1-chloro-2-propyl, 1-chloroethyl, 2-fluoroethyl, 1-chloro-2-propyl, 3-bromobutyl, 1,1,1-trifluoroisopropyl, Methoxyethyl, methoxyisopropyl, ethoxy-tert-butyl, methoxy-tert-butyl, optionally substituted cycloalkyl having 3 to 7, in particular 3 to 6 carbon atoms in the ring, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-chlorocyclohexyl, 2- ( trifluoromethyl) cyclohexyl; an optionally substituted aralkyl radical having 6 to 10 carbon atoms in the aryl part and 1 to 2 carbon atoms in the alkyl part, especially optionally substituted benzyl, ^ -phenylethyl; an optionally substituted aryl radical having from β to 20 carbon atoms, in particular optionally substituted phenyl, naphthyl; a ⁽ J) optionally substituted heteroaryl radical having 5 to 7, in particular 5 to 6, ring atoms, of which 1 to 3, in particular 1 to 2, heteroatoms which may be identical or different and are preferably oxygen, sulfur or nitrogen, for example an optionally sub- have pyridyl, pyrazolyl, thienyl, puryl or pyrimidinyl radicals.

R is, for example, an unbranched alkyl radical having 1 to 20 carbon atoms, a branched alkyl radical having 3 to 15 carbon atoms, a straight-chain or branched alkenyl or alkynyl radical having 3 to 15 carbon atoms or a cyclic alkyl or

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^v. - - 6 - OZ 0050/034586

Alkenyl radical having 3 to 10 ring carbon atoms or an alkanone radical, where each of the radicals may be optionally substituted. Examples of R 1 are: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, η-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, 2-pentyl, 3-pentyl, tert-amyl, neopentyl, 2-methyl-2-butyl, 3-methyl-butyl, 3-methyl-2-butyl, cyclopentyl, n-hexyl, 4-methyl-2-pentyl, 2,3-dimethylbutyl, 2-methyl-1- pentyi, 2-hexyl, 3-methyl-2-pentyl, 3-methylpentyl,

10 4-methylpentyl, 3-methyl-3-pentyl, 4,4-dimethylbutyl,

Cyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-octyl, 2-octyl, 3-octyl, 4-octyl, 5-octyl, 5-ethyl-2-heptyl, 2,6- Dimethyl-4-heptyl, 7-ethyl-2-methyl-4-nonyl, 2,4-dimethyl-3-pentyl, 3-methyl-2-heptyl, 5-ethyl-2-nonyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 6-ethyl-3-decyl, 6-ethyl-3-octyl, 2-methyl-2-pentyl, 2,3-dimethyl-2 butyl, 2-methyl-2-hexyl, 3-ethyl-3-pentyl, 3-methyl-3-hexyl, 2,3-dimethyl-pentyl-3, 2,4-dimethyl-2-pentyl, 2,2 , 3-trimethyl-3-butyl, 2-methyl-2-heptyl, 4-methyl-4-heptyl, 2,4-dimethyl-2-octyl, 1-methyl-1-cyclopentyl, 1-methyl-1-cyclohexyl , 1-ethyl-1-cyclohexyl, chloro-tert-butyl, 1,1-dichloro-2-methyl-2-propyl, 1,3-dichloro-2-methyl-2-propyl, 1-cyclohexyl

25 -1-ethyl, 2-chloroethyl, 2-chloropropyl, 3-chloropropyl,

1-chloro-2-propyl, 2-chlorobutyl, 2-chloro-2-methyl-3-propyl, 2-chloroethyl, 2-proporopropyl, 3-proporopropyl, 1-chloro-2-propyl, 2-fluorobutyl, 2 Fluoro-2-methyl-3-propyl, 2-bromomethyl, 3-bromopropyl, 4-chlorobutyl, 2-chlorocyclohexyl,

30 1,1,1-trifluoroisopropyl, hexafluoro-2-methylisopropyl,

Hexafluoroisopropyl, Hexachlorisopropyl, 1,2-Dibromallyl, 2,2,2-trifluoroethyl, l-chloro-butyn-2-yl-4, 3-Chlorbutin- _l_yl_H _j l-chloro-buten-2-yl-4, 2, 2,2-trichloroethyl, 1-chloropentin-2-yl-4, 2,2,2-tribromoethyl, 3,4,4-trichloro ·

35-buten-3-yl-2, 1-bromo-2-propyl, 1, S-

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* 3-butylbuten- _s- l-yl-4, allyl, propargyl, crotyl, butyn-2-yl-1-yl, methallyl, buten-1-yl-3, butyn-1-yl-3, butene 1 -yl-4, butyn-1-yl-4, 2-methylbutene-1-yl-3, 2-methylbutene-2-yl-1, 2-methyl-buten-2-yl-4, 3 Methyl-buten-1-yl-3>'5 * 3-methylbutyn-1-yl-3, 2-methylbut-1-yl-4, 2-ethyl

-hexen-2-yl-1, hexen-5-yl-1, εcencene-10-yl-l, 1-ethynylcyclohexyl, methoxyethyl, ethoxyethyl, 3-methoxy-propyl, methoxyisopropyl, 3-methoxybutyl, 1-methoxy-butyl -2, ethoxy-tert-butyl, methoxy-tert-butyl, cyclohexyloxy- ΓΛ'-10' -tert-butyl, 2-methoxy-butyl, 4-methoxy-butyl, fi-methyl-mercapto-ethyl, β- Ethylmercaptoethyl, 3-methyl-mercapto-propyl, 1-methylmercaptobutyl-2, methylmercapto-tert-butyl, 2-methylmercaptobutyl, 4-methyl-mercaptobutyl, 2-n-butoxyethyl, 2-ethoxypropyl, 3-ethoxy-2 propyl, 2-methylbutan-3-yl-2, 2-methyl-pentanone-4-yl-2,3-butanone-1-yl, 3-butan-2-yl, 2-propanone-1-yl, 2-pentanone-1-yl, Ν, Ν-dimethylaminoethyl; R 1 represents, for example, an optionally substituted aryl, arylalkyl, heteroaryl or heteroarylalkyl radical having 6 to 12 carbon atoms in the aryl or heteroaryl part and 1 to 3 carbon atoms in the alkyl part, for example an optionally substituted phenyl or naphthyl radical or an optionally substituted heteroaryl radical 5 to 6 ring atoms and 1 to 3, in particular 1 to 2 heteroatoms in the ring, which may be identical or different and are preferably oxygen, nitrogen or sulfur, for example a pyridyl, pyrazolyl or pyrimidinyl radical. ·

Preferred substituents of the aryl or heteroaryl radical include: halogen, in particular fluorine, chlorine or bromine; nitro; a straight-chain alkyl radical having 1 to 14, a branched or cyclic alkyl radical having 3 to 14 carbon atoms; an alkoxy or alkylthio radical having 1 to 5 carbon atoms, a haloalkyl, haloalkoxy,

23212 5 1

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^ Halogenalkylthio- or Halogenalkylsulfonylrest with up to 4 carbon atoms and up to 9 halogen atoms, in particular fluorine or chlorine; a formyl, cyano or thiocyanato group; an alkoxycarbonyl, dialkylketo, alkylcarbonyl, alkyl and dialkylcarbamoyl, acylamino or an alkylaminosulfonyl radical having 2 to 10 carbon atoms, for example a methoxycarbonyl, acetonyl, propionyl, Ν, Ν-dimethylcarbamoyl or a butyrylamino radical; an alkoxyalkyl or alkylthioalkyl radical having 2 to 6 carbon atoms, for example, an ethoxypropyl or a methylmercaptomethyl radical; an optionally substituted phenyl or phenylcarbonyl radical having 6 to 11 carbon atoms; an optionally substituted in particular in the 4-position aryloxy, arylalkyloxy or arylazo, for example, a 4- (4'-chlorophenoxy) -, 4- (2 ^f, 4 ^{-Dichlorphenoxy?)} - 4- ⁽¹ J 'trifluoromethylphenoxy ) Radical or a 4- (4'-chlorophenylazo) or 4- (3'-pluorphenylazo) radical; an optionally substituted arylthio, arylsulfinyl or arylsulfonyl radical; an optionally substituted

20 arylalkyl radical, in particular an unsubstituted

or substituted benzyl radical; a straight-chain alkenyl radical having 2 to 6 or a branched alkenyl radical having 3 to 7 carbon atoms; a straight-chain alkynyl radical having 2 to 4 or a branched alkynyl radical having 3 to

25 6 carbon atoms; fused rings, in particular

from the classes of aromatics and heterocycles, for example, fused optionally substituted benzo, benzofuran or Pyridinoreste.

6 7

R and R 'may together with the adjacent nitrogen atom denote an optionally substituted heterocyclic radical, for example a 3- to 7-membered heterocycle which optionally has one or more double bonds and further heteroatoms such as nitrogen,

35 contains oxygen or sulfur, for example one

232125 1

- 9 - ° · ² · 0050/034586

Pyrrolidinyl, 4-methylpiperazinyl, imidazolyl, 1,2,4-triazolyl, piperidinyl or 2,6-dimethylmorpholinyl.

Salts are, for example, the alkali metal (Na, K) or alkaline earth metal salts (Mg, Ca) of the carboxylic acids.

The reaction is conveniently carried out at a temperature of -80 to +120 C, preferably from -75 to +80 C, in particular from -70 to 3O ⁰ C, under atmospheric or superatmospheric pressure, continuously or discontinuously. It is expedient to use inert solvents under the reaction conditions. Examples of suitable solvents are: aromatic hydrocarbons, for example toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene; Halogenated hydrocarbons, in particular chlorohydrocarbons, for example tetrachlorethylene, 1,1,2,2- or 1,1,1,2-tetrachloroethane, amyl chloride, dichloropropane, methylene chloride, dichlorobutane, isopropyl bromide, chloroform, ethyl iodide, propyl iodide, carbon tetrachloride, 1,1,1 or 1,1,2-trichloroethane, trichlorethylene, pentachloroethane, 1,2-dichloroethane, 1,1-dichloroethane, n-propyl chloride, 1,2-cis-dichloroethylene, n-butyl chloride, 2-, 3- and iso-chloroethane. Butyl chloride, chlorobenzene, o-, p- and m-dichlorobenzene, o-, m-, p-chlorotoluene, 1,2,4- - trichlorobenzene; Ketones such as methyl ethyl ketone, acetone, diisopropyl ketone, diethyl ketone, methyl isobutyl ketone, mesityl oxide, acetophenone, cyclohexanone, ethyl isoanyl ketone, diisobutyl ketone, methylcyclohexanone, dimethylcyclohexanone; Esters such as methyl acetate, n-propyl acetate, methyl propionate, butyl acetate, ethyl formate, methyl phthalate, methyl benzoate, ethyl acetate, phenyl acetate; Nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; Sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, dimethylsulfone, Diäthylsülfon, methyl ethyl sulfone, tetramethylene sulfone; aliphatic or cycloaliphatic

232125 1

  - ^ -10-. O.Z. OO5O / O34586

phatic hydrocarbons, for example heptane, oC'-pinene, pinane, nonane, petroleum fractions boiling within a range from 70 to 190 ⁰ C., cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, ligroin, 2,2,4-trimethylpentane, 2,2, 3-trimethylpentane, 2,3,3-trimethylpentane, octane; N, N-disubstituted acid amides such as dimethylformamide, dimethylacetamide; and corresponding mixtures. Suitably, the solvent is used in an amount of 100 to 10,000 weight percent, preferably 500 to 2,000 Ge weight percent, based on starting material.

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

Suitable reaction accelerators are: activated carbon, boron trifluoride, aluminum or antimony halides such as chlorides or bromides, iron chloride, zinc chloride, aluminum oxide, titanium, tantalum, niobium, rhenium or molybdenum halides such as chlorides or bromides or oxychlorides.

It is generally used for 1 mole of the starting material II 0.8 to 20 mol, preferably 1 to 15 mol of hydrofluoric acid. However, if the hydrofluoric acid and / or the catalyst is to be used as solvent, the molar ratios given can be considerably exceeded, then amounts of from 10 to 100, in particular from 10 to 100, moles of hydrogen fluoride per mole of starting material II and / or suitably from 0.001 to 2, in particular 0.001 to 0.1 equivalents of accelerator per mole of starting material II.

The reaction can be carried out as follows: A mixture of starting material and hydrogen fluoride, given

Z ό 1 1 2 5 1

- 11 - O.Z. ΟΟ5Ο / Ο34586

if co-solvent is maintained at the reaction temperature for 0.1 to 60 hours. From the reaction mixture, the end product I is prepared in a conventional manner, e.g. separated by filtration and fractional distillation. But you can also pour the reaction mixture on ice and separate the organic phase or extract with a water-immiscible organic solvent.

In a preferred form of the method according to the invention defines at -80 to -4o ⁰ C anhydrous hydrofluoric acid before and slowly add the starting material II, in particular a solution thereof in an inert solvent, and carries out the reaction for 10 minutes to 15 hours, particularly during 10 minutes to 5 hours, through. The order of addition of the reactants can also be reversed by adding the gaseous hydrogen fluoride to the reactant.

The compounds of the formula I have a selective herbicidal activity. They are therefore suitable for use as plant protection products for controlling harmful plants in agricultural crops.

25 Example 1

In a stirred flask (fluorinated polyethylene) are added to a solution of 17 parts (parts by weight) 2- (4'-fluorophenoxy) -acrylic acid methyl ester in 100 parts of carbon tetrachloride with stirring and cooling to -65 C 10 parts of anhydrous hydrofluoric acid. The mixture is warmed to room temperature and the solvent and unused hydrofluoric acid are distilled off in vacuo over a condenser.

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Distillation of the residue gives 13 parts (70 % of theory) of methyl 2-fluoro-2- (4'-fluorophenoxy) propionate.

⁵⁶ ° ^C ·

5 Example 2

In a stirred flask, 30 parts of anhydrous hydrofluoric acid are added to a solution of 29 parts of 2 - ('2', 4'-Dlchlorphenoxy) -acrylic acid methyl ester in 100 parts of petroleum ether with stirring and cooling to -78 ° C. The reaction mixture is allowed to warm to room temperature and distilled under a slight vacuum, the solvent and the excess hydrogen fluoride. The residue is dissolved in petroleum ether, sodium fluoride is added and filtered off.

15 ^:

Distillation of the filtrate gives 24 parts (77 % of theory) of 2- (2 ', 4'-dichlorophenoxy) -2-fluoro-propionic acid methyl ester. Kp _{0) 1} 90 ⁰ C.

20 Example 3

In a stirred flask 89 parts of 2- (2 ^T , 4'-dichlorophenoxy) -acrylic acid are dissolved in 100 parts of methylene chloride and 80 parts of hydrogen fluoride with stirring and cooling to -65 C added. The mixture is warmed to room temperature and distilled off excess hydrogen fluoride. The crude product is stirred with η-hexane and filtered off. Yield: .86 parts (89 % of theory) of 2- (2 ', 4'-dichlorophenoxy) -

-2-fluorpropionsäure. Mp .: 88-9O ⁰ C.

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" Example 4

In a stirred flask to 14 parts of 2- (2 ^f , 4'-dichlorophenoxy) -acrylic acid at -65 ° C added 30 parts of anhydrous hydrofluoric acid, heated to room temperature with stirring and then distilled off the excess hydrogen fluoride. The product is recrystallized from η-hexane; Siert. Yield: 9 parts (59 % of theory) of 2- (2 ', 4'-dichlorophenoxy) -2-fluoropropionic acid. Mp .: 88-9O ⁰ C.

O ¹ °

The preparation process a is further illustrated by the examples of Table I.

20

25

30

35

232125 1

0.2. OO5O / O34586

CO CQ 0) -U, C -P SL, O Ή

ο «ο ω

(M

co

b o rH

C Φ

-P

co -P

Φ: O -H

Eh J ε

rh

CO

SlOrH C Φ

-P

CO +5 K) Ή

•H EC Φ CQ H b OH C Φ cd Ch H bO Ί-ι • Η CO O Φ H Eh <co Φ r \ t \ rh Φ I Φ X! • Η • Η CD Φ CX CQ CO

EC

OO

I • Η

cn

SC

5C O Oιη

CM O

O \ I CQ \ I CQ \ 1 1 cn I > (Q) \ Co) O V T rh rh ϋ O O

O O

O O

O O

O O

O O

CM SL · Φ O .P OJ Φ CM EC r \ r ** 1 O O O ί. CM 4-1> EC φ O CU

CM

O cn

LH

rH O

EC ϋ

O cn

CM

CM

EC ϋ

LfN CM

CM O O r-i ^ { ϋ O CM CM rc ϋ

O CM

OO CM

in

LT. CMLPi

cn

CM CM

OO CM

LPiCO

LJL

Κ "

UI

Table I : Port setting

example

to 5 to 6 to 7 to 8 to 9 too

Kp (mbar) ⁰ C

End product Pp ⁸ C

Yield % of theory

40 ^° C (0,1)

45 ° C

100 ° C (0.2) 101 ⁰ C (0.3)

1.4860

90-91 ⁰ C 52 ° C

70 62

75 60

71 79 45

UI O

O UO

-tr UI 00

23 2125 1

- 16 - OZ OO5O / O34586

~ Example 12

To a solution of 20.4 parts of imidazole in 150 parts of tetrahydrofuran is added dropwise at 10 to 20 ⁰ C 8.9 parts of thionyl chloride. It is stirred for 30 min. at room temperature, filtered off and added to the filtrate with 19 parts of 2- (2 ', 4'-dichloro phenoxy) -2-fluoropropionic acid. The mixture is stirred for 2 hours at room temperature and then 5.1 parts of 2-propanethiol and stirred for 6 hours at room temperature. After concentration, the reaction mixture is taken up in methylene chloride, washed twice with water, the organic phase is dried with magnesium sulfate and the solvent is removed. This gives 21 parts (90 % of theory) of 2- (2'-4'-dichlorophenoxy) -2-fluoropropionic isopropylthio-ester; nf =

15 1,5272.

As further herbicidal active compounds of the general formula may be mentioned by way of example:

Ui

cn

^r Example number

13

16 17

19 20

21

κι ο

ul

Mp K [ ⁰ C]

Cl

Cl

0 0

0 0

0 0 0

Cl

O-CH

\ -

Cl

⁰ XJ

n * ⁰ = 1.5070

Cl

CH, O-CH ₂ CH-O-VL Cl

0-CH ₂ CH ₂ O

Cl

CP

OO Ul O \ OU) 4> Ul CD

he"

IO

Example number

22

23

24 25 26 27

28 29

30

31 32 33

^RJ

Il

Il

F ₃ C

κ "

Gi

CH

CH '.

Il

\> C1

NH-tert. C ₁₄ H ₉

-SCH

\\ ci

O-CH 0-C ₂ H ₅

O-CH

OC ₂ H ₅

Fp, Kp [ ⁰ C]

) -90

= 1.5826

OO I

O O UI O N O U)

00 CTv

ro

OJ

ro

cn

2321

25

- 19 -

0.2.0050 / 034586

ο ο CVi

OO

ο. αIl

CM CM Q

10

fO K ro

20

CVJto

25

30

35

Φ • Η

co • η

 aro

in ro

ro

OD CTi O

ro ro

CM

ro

Example number

46

ro

Cl

Gi

R-

SC ₃ H ₇

OCH _n

ul

O.

PP, Kp rc]

ro> o

48 49

50

51 52

53 54

55 56

ti Il

F /

Il ti It NH-tert.CH _q ti It Il NH-C (CH ₃ ) ₂ C = CH Il It It OCH It ti It Il ti. It OC ₂ H ₅ NH-tert.C ₄ H ₉ It It It OC ₂ H ₅ It It It 0-1-C ₃ H ₇ Cl

¹¹ 0-

ro o

O O

ul

O La)

J = T

Ul OO ON

OH

Example number

58 59 60 6l 62 63

64 65 66

67 68

^RJ

Il Il Il

ro

II

IM O

ul

Il Il Il Il Il Il Il Il Il

CH.

SCH

S-Z ^ N-Cl

OCH

OC ₂ H ₅

ul

Pp, Kp [ ⁰ C]

ro

OO UI O \ O LO 4> UI

SCH.

cn

to

cn

^r example

Nununer

69

70 71 72 73 71 75

77 7879 80

81 82

Il Il Il Il

Il

η '

Il Il Il Il

Il

a »

Il Il Il

Il

SC ₂ H ₅

S-tert.Cj OH OCH.

N (CH:

ΝΗ- ^ 3) NH-tert.C;

OH

OC ₂ H ₅

Λ-ci

NHCH

Pp, Kp [ ⁰ C]

ro ro

IN THE

O O

O co

4> UI CO

OJ

ro

ro cn

example

number

^RJ

ro tn

R-

Pp, Kp [ ⁰ C]

ro

co ro

83

8Ί 85

86

87

91 92

93 9 ¹ I

Il

" ^C3 \ \\ _ Il 88 Cl-4 Cl 11 89 90 7 ~ \ z

Il

Il

Il

Il

Il

I) Il

Il

11

Il

OCH.

OC ₂ H ₅ SCH,

s-C ^ Vci c:

S-CH ₂ - // j0

OH

0-1-C ₃ H ₇

SOIL · N (CH

ro ι

O O Ul O \ O U) 4> Ul 00

CJ

cn

• "Example number

96 97

99 100

101

102

103 101

κ »uv

Il

It Il

It's it

Il

Il

Il It

\ -

OH

OCH,

0-1-C ₃ II ₇

cn

Pp, Kp C ⁰ C]

0-CH ₀ CH ₂ O

SCH SC ₂ H ₅

76-77

ro

4 = ·

O VJI O \ O Lu 4> VJl

00 σ »

cn

^r Example ,, Number

105

106 107 108

109

110 111

112

113 11 H

ro Ui

Cl

ci-f \ o- ( '

Ν "

R '

OCH ₃

OCH, OCH

OH OCH

^SCH 2 "Vy" ^C3L

Pp, Kp [ ⁰ C]

VJI

O O cn O • V. O U)

J>

CD

Example number

115

116

U "

Cl

N «JH ₃ ) ₂

OCH

Pp, Kp [ ⁰ C]

ro

ro cn

117

118 119

120 121

122 123

It Il

Cl

C

Il

Il

NH,

SC ₂ H ₅ OH

OCH

OCH

OH OCII,

ν / '

ro

O O Ul O \ O to 4> Ul 00

Ui Ul

"" Example number

ro

κ "

R-

UI

Κρ, Ρρ [ ⁰ C]

ro co

ro

125 126

Cl Cl - //

H H

0 0

OCH.

OH

ro

cn

ro

O O UI O • χ O U) 4> Ul 00

σ "

232125 1

- 28 - OZ 0050/034586

The compounds are applied by spraying or dusting the plants or soil with the active ingredients.

The new substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The forms of application depend entirely on the intended use; they should in any case ensure a fine and even distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or excipients, if appropriate using emulsifiers and dispersants, it being possible to use other organic solvents as auxiliary solvents in the case of the use of water as diluent. Suitable auxiliaries are essentially: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), amines or amides (eg ethanolamine, dimethylformamide) and Water; Carriers such as ground natural minerals, e.g. Kaolins, clays, talc, chalk and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifying agents, such as non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohols-ethers, alkyl sulfonates and arylsulfonates) and dispersants, such as lignin, sulfite liquors and methyl cellulose.

The herbicidal compositions contain from 0.1 to 95% by weight of active substance, preferably from 0.5 to 90% by weight .

The compositions or the ready-to-use preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules are known in the art

23212 5V

- 29 - ° · ² · OO5O / O34586

Applied, for example, by spraying, atomizing, dusting, scattering or pouring.

embodiments

Example I * *

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone, giving a solution which is suitable for use in the form of very small drops.

Example II

10 parts by weight of compound 2 are 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-monoc-ethanolamide, 2 parts by weight of CaI cium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the Aniagerungsproduktes of 40 moles of ethylene oxide to 1 mole of castor oil.

Example III

20 parts by weight of compound 2 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct. tes of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene

30 lenoxid to 1 mole of castor oil.

Example IV

20 parts by weight of compound 3 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of

2321251

  : ... -. , , ,:. -30- 0.2. 0050/034586

^r parts by weight of a mineral oil fraction of boiling point 210 to 28O ⁰ C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil.

5 Example V

80 parts by weight of the active compound 1 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid / 10 parts by weight of the sodium salt of a lignosulfonic acid from a SuIfit waste liquor and 7 parts by weight of powdered silica gel and ground in a hammer mill.

Example VI

15 '

5 parts by weight of compound 1 are intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust containing 95 weight percent of the active ingredient.

Example VII

30% by weight of compound 1 is intimately mixed with a mixture 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. This gives a preparation of the active substance with good adhesion.

30 Example VIII . ,

40 parts by weight of the active compound 1 with 10 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water

232125 1

- 31 - ° · ² · 0050/034586

intimately mixed. A stable aqueous dispersion is obtained.

Example IX 5

20 parts of the active compound 1 are intimately mixed with 12 parts of calcium dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of phenol sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. This gives a stable oily dispersion.

The effect of the new Pluoralkancarbonsäureverbindungen on the growth of desirable and undesirable plants is demonstrated by greenhouse experiments:

The culture containers used were plastic flower pots with a content of 300 cnT and loamy sand with about 1.5% humus as substrate. The seeds of the test plants separated by species are flat e.ingesät. Immediately thereafter, during pre-emergence treatment, the active ingredients were applied to the surface of the earth. They were suspended or emulsified in water as distributing agents and sprayed by means of finely distributing nozzles. This application method is an application rate corresponding to 3.0 kg total active ingredient / ha. After application of the agents, the vessels were lightly rained to induce germination and growth. Thereafter, the containers were covered with transparent plastic hoods until the plants had grown. 30 This cover caused a uniform germination of the test plants, as long as it was not affected by the active ingredients. For the postemergence treatment, the test plants were grown depending on the growth form only to a stature height of 5 to 20 cm and then treated. For postemergence treatment were either sown directly and

232125 1

'''- 32 - O.2-OO5O / O3M586

selected in the same vessels grown plants, or they were first grown separately as seedlings and transplanted a few days prior to treatment in the test tubes. The application rates for post-treatment were also 3) 0 kg total active substance / ha for some compounds. Further examples were used at 1.0 kg / ha and 2.0 kg / ha of total active ingredient. The dimethylamine salt of 2,4-dichlorophenoxy-.alpha.-propionic acid (A) at 2.0 kg / ha, calculated as acid, and the dimethylamine salt of 2-methyl-4-chlorophenoxy-propionic acid (B) as 1, 0 kg / ha calculated as acid. A cover was omitted in the post-emergence treatment. The setup of the experiments was carried out in the greenhouse, with heat-loving species warmer areas (20 to 30 ⁰ C) and for those temperate climates 15 to 25 C were preferred. The trial period lasted for 3 to 4 weeks.

During this time, the plants were maintained and their response to each treatment evaluated. A scale of 0 to 100 has been used. 0 means no damage or normal course and 100 no emergence of the plants or complete destruction of at least the above-ground parts.

The results show that the compounds exert a considerable effect in pre-emergence application. In the preferred postemergence application, the herbicidal activity is similar, in some undesirable plants better than in the known comparison means. Particularly noteworthy

30 is the more favorable compatibility of the new compounds for crops.

23212 5 1

- 33 - O-2 · ΟΟ5Ο / Ο34586

If certain crop plants are somewhat sensitive to the active substances, application techniques may be used in which the herbicidal agents are directed by means of sprayers so that the leaves of sensitive crops are not affected if possible, while on the leaves underneath growing undesirable plants or the uncovered floor surface

_; , long (post-directed, lay-by). Considering the good compatibility and the versatility of the application

C \ 10 methods, the herbicides of the invention can still be used in a further large number of crops to eliminate undesirable plant growth. The application rates can vary between 0.1 and 15 kg / ha and more.

For example, the following cultures may be considered:

20

25 30 35

κ>

Botanical name

German name

English name

Alllum cepa Pineapple comosus Arachis hypogaea Asparagus officinalis Avena satlva Beta vulgaris spp. altisslma Beta vulgaris spp. rapa Beta vulgaris spp. brassica napus var. napus Brasslca napus var. napobrasslca Brasslca napus var. rapa Brasslca rapa var. sllvestrls Camellia slnensls Carthamus'tlnctorlus Cary illlnolnensls Citrus limon Citrus maxima Citrus reticulata Citrus slnensls

Coffea arabica (Coffea canephora, Coffea llberlca)

Cucuml's melo

onion

pineapple

Peanut

asparagus

oats

sugar beet

mangel

Red beet

rape

Swede - ^:

White turnip

rape

Teestrauch

Safflower - safflower

Pecan

lemon

grapefruit

tangerine

Orange, orange

coffee

melon

onions

pineapple

peanuts

asparagus

sugarbeets

fooder beets

table beets, red beets

rape seed

turnips

tea plants safflower pecan trees lemon grapefruit

orange trees coffee plants

melons

J = · I

O O VJl

O UO

J = -

Ul OO

he"

cn

cn

^Γ Botanical name

Cucumis sativus Cynodon dactylon

Daucus carota Elaeis guineensis Fragaria vesca Glyoins max

Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) Helianthus annuus Helianthus tuberosus Hevea brasiliensis Hordeum vulgare Humulus lupulus Ipomoea batatas Juglans regia Lactua sativa Lens culinaris Linum usitatissimum Lycopersicon lycopersicum Malus spp.

tn

ui

German name

Cucumber bermuda grass

Carrot oil palm strawberry soybean

cotton

sunflower

Jerusalem artichokes

Parakatuschukbaum

barley

hop

sweet potatoes

walnut tree

lettuce

lens

flax

tomato

Apple

English name

cucumber

Bermuda grass in turfs and lawn

carrots oil palms strawberries soybeans

cotton

sunflowers

rubber plants

barley

sweet potato

walnut trees

lettuce

lentils

tomato

apple trees

UJ

O O

VJL

Oh yes

J = -

VJI OO

Botanical name ο »

Manihot esculenta Medicago sativa Metha piperlta Musa spp.

Nicotiana tabacum (N. rustica) Olea europaea Oryza sativa Panicum miliaceum Phaseolus lunatus Phaseolus mungo Phaseolus vulgaris

Pennisetum glaucum

Petroselinum crispum spp. tuberosum Picea abies Abies alba Pinus spp

 Pisum sativum Prunus avium Prunus domestica

German name

English name

manioc

alfalfa

peppermint

Fruit and flour banana

tobacco

olive tree

rice

Rispenhirse

butterbean

black gram

bush beans

Perl or cattail millet

root parsley

Rotfichte

white fir

pine

garden pea

sweet cherry

plum

cassava

alfalfa (lucerne)

peppermint

banana plants

tabacco

olive trees rice

lima bean mungbeans

snapbeans, green beans, dry beans

parsley

Norway spruce

pine trees

English peas

cherry trees

plum trees

U)

O O Ui O \ O U) j = -

UI OO

ι »Ul

Botanical name German name

English name

Prunus dulcis Prunus persica Pyrus communis Ribes sylvestre Ribes uva-crispa Ricinus communis Saccharum officinarum Secale cereale Sasamum indicum Solanum tuberosum Sorghum bicolor Sorghum dochna Spinacia oleracea Theobroma cacao Trifolium pratense Triticum aestivum Vaccinium c'orymbosum Vaccinium vitis-idaea Vicia faba Vigna sinensis (V unguiculata) Vitis vinifera Zea mays

almond almond trees ₍ peach peach trees U) pear pear trees I Red currant red currants gooseberry castor-oil plant sugarcane sugar cane rye rye sesame Sesame ρ potato Irish potatoes sorghum sorghum O O r i sweet sorghum VJl O spinach spinach O U) cacao cacao plants UI oo Red clover red clover σ \ wheat wheat Cultivated blueberry blueberry Preißelbeere cranberry horse beans tick beans cowpea cow peas grapevine grapes Corn Indian corn, sweet corn maize _ «

232125

- 38 - 0.2. OO5O / O34586

To broaden the spectrum of action and to achieve synergistic effects, the new fluoroalkanecarboxylic acid compounds can be mixed both together and with numerous representatives of other herbicidal or growth-regulating active substance groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofurane derivatives, cyclohexane-1 are used as mixing partners , 3-dione derivatives and others. A number of active ingredients which, together with the new compounds for various applications yield useful mixtures, are given by way of example:

Methyl 2- Naphthoxyacetate 2- (2-Methylphenoxy) propionic acid (salts, esters, amides) 2- (4-Chlorophenoxy) propionic acid (salts, esters, amides)

2- (2,4-dichlorophenoxy) propionic acid (salts, esters, amides) 20 2- (2,4,5-trichlorophenoxy) -propionic acid (salts, esters,

Amides) 2- (2-methyl-4-chlorophenoxy) -propionic acid (salts, esters, amides) 4- (2,4-dichlorophenoxy) -butyric acid (salts, esters, amides): 4- (2-methyl-4-) chlorophenoxy) butyric acid (salts, esters, amides) Cyclohexyl-3- (2,4-dichlorophenoxy) -acrylate 9-Hydroxyfluorene-carboxylic acid- (9) (salts, esters) 2,3j6-Trichlorophenylacetic acid (salts, esters ) 4-chloro-2-oxo-benzothiazolin-3-yl-acetic acid (salts, esters) gibelleric acid (salts) disodium methylarsonate monosodium salt of methylarsonic acid N-phosphono-methyl-glycine (salts)

232125 1

- 39 ° - ^ζ · ΟΟ5Ο / Ο34586

* "N, N-Bis- (phosphono-methyl) -glycine (salts) 2-Chloroethanephosphonic acid 2-chloroethyl ester Ammonium ethyl-carbamoyl-phosphonate Di-n-butyl-1-n-butylamino-cyclohexyl-phosphonate Trithiobutyl phosphite

0.0-diis- ^3- propyl-5- (2-benzosulfonylamino-ethyl) -phosphordithioate

2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,4,4,4-tetraoxyde 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -l, 3 , 4- C j 10 -oxadiazolone- (2)

^, S-dichloro-S-trifluoromethyl-benzimidazole (salts) l, 2,3,6-tetrahydropyridazine-3,6-dlone (salts) succinic mono-N-dimethylhydrazide (salts) (2-chloroethyl) -trimethyl- ammoniuinchlorid

15 (2-Methyl-4-phenylsulfonyl) -trifluoromethanesulfonanilide 1-methyl-1-di-methyl-1-diisopropyl-S-indanyl-ethyl ketone, sodium chlorate Ammonium rhodanide Calcium cyanamide

5-Amino-4-chloro-2-phenyl-3 (2H) -pyridazinone 5-Amino-4-bromo-2-phenyl-3 (2H) -pyridazinone 5-Amino-4-chloro-2-cyclohexyl-3 ( 2H) -pyridazinone 5-amino-4-bromo-2-cyclohexyl-3 (2H) -pyridazinone

5-Methylamino-4-chloro-2- (3-trifluoromethyl-phenyl-3 (2H) -pyridazinone

5-methylamino-4-chloro-2- (3 ^ _J ^, ß, ß-tetrafluoroethoxyphenyl) - -3 (2H) -pyridazinone

30 5-Dimethylamino-4-ehlor-2-phenyl-3 (2H) -pyridazinone 4,5-Dimethoxy-2-phenyl-3 (2H) -pyridazinone 4,5-Dimethoxy-2-cyclohexyl-3 (2H) - pyridazinone 4,5-Dimethoxy-2- (3-trifluonne-3'-phenyl) -3 (2H) -pyridazinone

23212 5 1

-, · · · ·; ; - 40 - O.Z. OO5O / O34586

^l "5-Methoxy-4-chloro-2- (3-trifluoromethylphenyl) -3 (2H) -pyri-" * dazynone 5-araino-4-bromo-2- (3 "methylphenyl) -3 (2H) -pyridazinone

3- (1-Methylethyl) -1H-2, 1,3-benzothiadiazine B * 4 (3H) -one-2,2-dioxide and salts

3- (1-Methylethyl) -8-chloro-1H-2,1,3-benzothiadiazine-4 (3H) -one-2,2-dioxide and salts

3- (1-Methylethyl) -8-fluoro-1H-2, 1,3-benzothiadiazine-4 (3H) -10 -one-2,2-dioxide and salts

3- (1-Methylethyl) -8-methyl-1H-2, 1,3-benzothiadiazine-4 (3H) -one-2,2-dioxide and salts

1-Methoxymethyl-3- (1-methylethyl-2,2,3,1-benzothiadiazine-4 (3H) -one-2,2-dioxide

l-methoxymethyl-8-chloro-3- (l-inethylethyl) -2, l, 3-benzothia-

diazine-4 (3H) -one-2,2-dioxide

l-methoxymethyl-8-fluoro-3- (1-methylethyl) -2,1,3-benzothia-

dazine-4 (3H) -one-2,2-dioxide l-cyano-8-chloro-3- (1-methylethyl) -2, l, 3-benzothiadiazine-4 (3H) -one-2,2- dioxide

1-cyano-8-fluoro-3- (1-methylethyl) -2,1,3-benzothiadiazine-4 (3H) -one-2,2-dioxide

1-cyano-8-methyl-3- (1-methylethyl) -2,1,3-benzothiadiazine-25- (3H) -one-2,2-d oxide

; l-cyano-3- (l-methylethyl) -2, l, 3-benzothiadiazin-4 (3H) -one

-2,2-dioxide '

l-azidomethyl-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -

-on-2,2-dioxide 30 3- (1-methylethyl) -1H-pyrldino-C3,2-e] 2, 1,3-thiadiazine (4) -

-one-2,2-dioxld

N- (1-ethyl-propyl) -2,6-dinitro-3,4-dimethylmethanol N- (1-methylethyl) -N-ethyl-2,6-dinetro-4-trifluoromethylaniline

uj

232 125 1

= "- 41 - Ο · ² · ΟΟ5Ο / Ο34586

^r Nn.propyl-N-.beta.-chloroethyl-2,6-dinitro-4-trifluoro-ethyl-aniline

N-n.propyl-N-cyclopropylmethyl-2,6-dinitΓΓ-4-trifluoromethyl-aniline ^

5 * N-bis (n.propyl) -2,6-dinitro-3-amino-4-trifluoromethylanilide

N-bis (n.propyl) -2 _J 6-dinitΓ0-4-methyl-aniline N-bis (n.propyl) -2,6-dinitro-4-methylsulfonyl-aniline N-bis- (η.propyl ) -2,6-dinitro-4-arainosulfonyl-aniline Bis (β-chloroethyl) -2,6-dinitro-4-methylaniline N-ethyl-N- (2-methylallyl) -2,6-dinitro- 4-trifluoromethylaniline

N-methylcarbamic acid 3,4-dichlorobenzyl ester N-methylcarbamic acid 2,6-di-tert-butyl-4-methylphenyl

ester N-phenylcarbamic acid isopropyl ester

N-3-Fluorphenylcarbaminsäure-3-methoxypropyl-2-acetate

N-3-Chlorphenylcarbaminsäure isopropyl ester 20 ^N-3-chloro> phenylcarbamic-butyn-l-yl-3-ester

N-3-Chlorphenylcarbaminsäure-4-chloro-butyn ^ -2-yl-l-ester ·

N-3,4-Dichlorphenylcarbaminsäure-methylester

N- (4-amino-benzenesulfonyl) -carbamic acid methylester

0- (N-phenylcarbamoyl) -propanone oxime 25 N-ethyl-2- (phenylcarbamoyl) -oxypropionic acid amide 3'-N-isopropylcarbamoyloxy-propionic acid anilide

Ethyl N- (3- (N'-phenylcarbamoyloxy) phenyl) carbamate Methyl N- (3- (N'-methyl-N'-phenylcarbamoyloxy) phenyl) carbamate

Isopropyl-N- (3- (N'-ethyl-N'-phenylcarbamoyloxy) phenyl.) -

carbamate

Methyl N- (3- (N ^T -3 -methylphenylcarbamoyloxy) -phenyl) -car-

bamat 35

232125

- 42 - ·. O.Z. OO5O / O3M586

^r Methyl N- (3- (N'-4-fluorophenylcarbanoyloxy) phenyl) carbamate Methyl N- (3- (N, ¹ -chloro-4-fluorophenylcarbamoyloxy) -phenyl) carbamate

Ethyl N- (3- (N'-3-chloro-4-fluorophenylcarbamoyloxy) -phenyl) -5-carbamate

Ethyl-N- (3- (N'-3,4-difluorphenylcarbamoyloxy) phenyl) carbamate

Methyl N- (3- (N'-3,4-difluorophenylcarbamoyloxy) -phenyl) -carbamate '·

N-3- (4-Pluorphenoxycarbonylamino) -phenylcarbaminsäure-

methyl ester __

N-3- (2-Methylphenoxycärbonylamino) -phenylcarbaminsäure-

ethyl ester 15 N-3- (4-fluorophenoxycarbonylamino) phenylthiolcarbamic acid

raethylester

 N-3- (2,4,5-trimethylphenoxycarbonylamino) phenylthiolcarbamine

acid methylester

N-3- (phenoxycarbonylamino) phenylthiolcarbamic acid methyl ester

N, N-Diethyl-thiolcarbamic acid p-chlorobenzyl ester Ν, Ν-di-n-propyl-thiocarbamic acid ethyl ester

N, N-di-n-propyl-thiolcarbamic acid n-propyl ester 25 N, N-di-isopropyl-thiocarbamic acid-2 _J 3-dichloroallyl ester N, N-di-isopropyl-thiocarbamic acid-2 _} 3,3-trichloroallyl

ester

Njn-di-isopropyl-thiolcarbaminsäure-S-methyl ^ -isoxazolyl-

methylester 30 N _J N-di-isopropyl-thiolcarbaminsäure-3-ethyl-5-isoxazolyl

methyl ester N, N -di-sec-butyl-thiolcarbamic acid ethyl ester N, -di-sec-butyl-thiolcarbamic acid benzyl ester

Ethyl N-ethyl-N-cyclohexyl-thiocarbamate 35

232125 1

, Z. OO5O / O34586

"" N-ethyl-N-bicyclo- [2,2,1] -heptyl-thiocarbamic acid

ethyl ester ·

S- (2 _J 3-dichloroallyl) - (2,2,4-trlmethyl-azetidin) -l-carbo-

thiolate 5, S- (2,3,3-trichloroallyl) - (2,2,4-trimethyl-azetidine) -1-carbo-

thiolate

S-ethyl-hexahydro-1-H-azepine-1-carbothiolate S-benzyl-S-methylhexahydro-1H-azepine-1-carbothiolate S-benzyl ^^ - dimethylhexahydro-1H-azepine-1-carbothiolate S-ethyl-S -methylhexahydro-1H-azepine-1-carbothiolate N-ethyl-Nn-butyl-thiolcarbamic acid n-propyl ester

N, N-dimethyl-dithiocarbamic acid 2-chloroallyl ester N-methyl-dithiocarbamic acid sodium salt

Trichloroacetic acid sodium salt 15 οί, ύί-Όί chloropropionic acid sodium salt o / j ^ -dichlorobutyric acid sodium salt

Oi ₃ methyl , ß, ß-Tetraf luorpropionsäure sodium salt e ^ -methyl, "f, ß-dichloropropionic acid sodium o (chloro-ß- (4-chlorophenyl) -propionic acid methyl ester Oiijß-dichloro-ß-phenylpropionäure-methyl ester

Benzamido-oxyacetic acid 2,3 j 5-Triiodobenzoic acid 2,3,6-trichlorobenzoic acid

2,3,5,6-tetrachlorobenzoic acid 25 2-Methoxy-3,6-dichlorobenzoic acid 2-Methoxy-3,5,6-trichlorobenzoic acid 3-Amino-2,5,6-trichloro ^> benzoic acid

OjS-dimethyl-tetrachloro-thioterephthalate.;

Dimethy1-2,3,5,6-tetrachloro-terephthalate Disodium 3,6-endoxohexahydrophthalate iJ-Amino-S ^^ - trichloro-picolinic acid (salts) 2-cyano-3- (N-methyl-N-phenyl ) -amino-acrylic acid ethyl ester 2- [4- (4 -Chlorphenoxy ^f) phenoxy] -propionsäureisobutylester 2 - C 4 - (2 ', 4'-Dichlorphenöxy) -phenoxy] -propionic acid methyl ester

(Salts, esters, amides) (Salts, esters, amides) (Salts, esters, amides) (Salts, esters, amides) (Salts, esters, amides) (Salts, esters, amides)

232125 1

: .-: .-: ·. - 44 - 0.2- OO5O / O3A586

^r 2- [4- (4'-TrifluomethylphenoxyJ-phenoxy-propionic acid methyl ester

2- [4- (2'-Chloro-4- ^t- trifluorophenoxy) -phenoxy] -propionic acid-sodium salt · -

5 2- [4- (3 ', 5'-dichloropyridyl-2-oxy) -phenoxy] -propionic acid sodium salt

2- (N-benzoyl-3,4-dichlorophenylamino) -propionic acid ethyl ester

2- (N-Benzoyl-3-chloro-4-fluorophenyl-amino) -propionic acid methyl ester

2- (N-benzoyl-3-chloro-4-fluoro-phenylamino) -propionic acid iso

propyl ester . "c

2-Chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-Chloro-4-ethylamino-6- (amino-2- ^f- propionitrile) -l, 3,5-triazine

2-chloro-4-ethylamino-6-2-methoxypropyl-2-amino-l, 3, 5- triazine

2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1, 3,5-triazine 2-chloro-4,6-bisethylamino-1, 3,5-triazine 2-chloro-4, 6-bisisopropylamino-l, 3,5-triazine

2-Chloro-4-isopropyl-amino-6-cyclopropylamino-1,3,5-triazine

2-Azido-4-methylamino-6-isopropylamino-l, ^3,5-tr> iazin 2-methylthio-4-isopropylamino-6-ethylamlno-l, 3,5-tΓiazin 25 2-Methylthio-4-ethylamino-6 -teΓt.butyl-amino-1, 3,5-triazine. ^ ^ Methylthio-jo-bisethylamino-l, 3,5-triazine

2-methylthio-4,6-bisisopropylamino-l, 3,5-triazine

2-methoxy-4-ethylamino-6-isopropylanlino-l ₃ 3,5-triazine 2-methoxy-4,6-bisethylamino-l, 3,5-triazine

2-methoxy-4,6-bisisopropylamino-1,3,5-triazine. , 4-amino-6-tert-butyl-3-methylthi9-4,5-dihydro-l, 2,4-TRIA

zin-5-one

4-amino-6-phenyl-3-methyl-4,5-dihydro-l _J, 2,4-triazin-5-one 35

232125 1

- 45 - ° · ² - 0050/034586

* "M-Isobutylideneamino-O-tert-butyl-S-methylthio-1S-dihydro-1,2,4-triazin-5-one

-dione

S-tert-butyl-S-chloro-o-methyluracil 3-tert-butyl-5-bromo-6-methyluracil S-isopropyl-S-bromo-o-methyluracil 3-sec. Butyl-S-bromo-o-methyluracil 3- (2-Tetrahydropyranyl) -5-chloro-6-methyluracil 3- (2-Tetrahydropyranyl) -5,6-trimethylenuracil

2-Methyl-4- (3'-trifluoro-ethyl-phenyl) -tetrahydro-1,2,4-oxa-15-diazine-3,5-dione

2-methyl-4- (4'-fluorophenyl) tetrahydro-l, 2,4-oxadiazinetrione

-3,5-dione

3-amino-l, 2,4-triazole

l-allyloxy-l- (4-broraphenyl) -2- [l ', 2', 4'-triazolyl (l ^f) -] - ethane 20 (salts)

l- (4-chlorophenoxy-3 _J 3-dlmethyl-l (lH-l, 2 ₁ 4-trlazol-l-yl) -

-2-butanone

N, N-diallyl chloroacetamide N-isopropyl-2-chloroacetaniline N- (1-methyl-propyn-2-yl) -2-chloroacetanilide

2-methyl-6-ethyl-N- (propargyl) -2-chloracetanllid

2-methyl-6-ethyl-N- (ethoxymethyl) -2-chloracetanllid

2-methyl-6-ethyl-N- (2-methoxy-1-methylethyl) -2-chloroacet-30 anil id

2-methyl-6-ethyl-N- (isopropoxycarbonylethyl) -2-chloracet-

anilide

2-methyl-6-ethyl-N- (4-methoxypyrazole-l-yl-methyl) -2-chloro-

acetanilide. ,

232125 1

- 46 - OZ 0050/034586

* "2-Methyl-6-ethyl-N- (pyrazol-1-ylmethyl) -2-chloroacetanilide

2,6-Dimethyl-N- (pyrazol-1-ylmethyl) -2-chloroacetanilide 2,6-Dimethyl-N- (4-methylpyrazol-1-ylmethyl) -2-chloroacet-5-anilide

2, 6-Dimethyl-N- (1,2,4-triazol-1-ylmethyl) -2-chloroacetanilide

2,6-Dimethyl-N- ( _3J5 -dimethylpyrazol-1-ylmethyl) -2-chloroacetanilide

10 2,6-dimethyl-N- (1,3-dioxolan-2-ylmethyl) -2-chloroacetanilide

2,6-Dimethyl-N- (2-methoxyethyl) -2-chloroacetanilide 2,6-Dimethyl-N- (i.sobutoxymethyl) -2-chloroacetanilide 2 _} 6-Diethyl-N- (methoxymethyl) -2-chloroacetanilide 2 , 6-diethyl-N- (n-butoxymethyl) -2-chloroacetanilide 2,6-diethyl-N- (ethoxycarbonylmethyl) -2-chloroacetanilide

2,3,6-trimethyl-N- (pyrazol-l-yl-methyl) -2-chloroacetanilide

2,3-dimethyl-N- (isopropyl) -2-chloroacetanilide 2,6-diethyl-N- (2-n-propoxyethyl) -2-chloroacetanilide

2- (2-Methyl-4-chlorophenoxy) -N-methoxy-acetamide 2- (-naphthoxy) -N, N-diethylpropionamide 2,2-diphenyl-N, N-dimethylacetamide oi- (3,4,5-tribromopyrazole -l-yl) -N, N-dimethylpropionamide N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide N-1-naphthylphthalamic acid

Propionic acid 3,4-dichloroanilide Cyclopropanecarboxylic acid 3,4-dichloroanilide Methacrylic acid 3,4-dichloroanilide 2-Methylpentanecarboxylic acid 3j4-dichloroanilide 5-Acetamido-2,4-dimethyltrifluoromethane-sulfonanilide 5-Acetamido-4-methyl-trifluoromethane-sulfonanilide

2-Propionyl-amino-4-methyl-5-chloro-thiazole 35 O- (methylsulfonyd-glycolic acid N-ethoxyme-thy 1-2,6-dimethyl-

232125 1

- 47 - ° · ^Ζ · ΟΟ5Ο / Ο34586

anilide

0- (Methylaminosulfonyl) -glycolic acid N-isopropylanilide 0- (i-propylaminosulfonyl) -glycolic acid N-butyn-l-yl-3 -anilide 0- (methylaminosulfonyl) -glycolic acid hexamethyleneimide

2,6-dichloro-thiobenzamide 2,6-dichlorobenzonitrile SjS-dibromo-^ -hydroxy-benzonitrile (salts)

3,5-Diiodo-4-hydroxy-benzonitrile (salts); 3,5-dibromo-4-hydroxy-0-2,4-dinitrophenylbenzaldoxime (salts) 3,5-dibromo-4-hydroxy-0-2-cyano -4-nitrophenylbenzaldoxim

(Salts) pentachlorophenol sodium salt

2,4-dichlorophenyl-4'-nitrophenyl ether 15 2,4,6-trichlorophenyl-4'-nitrophenyl ether 2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether

2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether

2 _J 4'-Dinitro-4-trifluoromethyl-diphenyl ether

_2i 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-

ethers (salts)

2,4-dichlorophenyl-3'-methoxycarbony1-4'-nitro-phenyl ether 2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione 2- (3-tert .Butylcarbamoyl-oxyphenyl) _-4-methyl-l> 2.4 oxadiazinetrione

zolidin-3,5-dione

2- (3-iso-propylcarbamoyl-oxyphenyl) -4-methyl-l, 2,4-oxadiazinetrione

zolidin-3j5-dione 30 2-phenyl-3, 1-benzoxazinone- (4)

(4-bromophenyl) -3,4,5,9,10-pentaazatetracyclo-C5,4,1,0 » ^J

0, ^{8 '11} ] -dodeca-3,9-diene

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methane

sulfonate

23212 5 1

  ν -48- 0.2. ΟΟ5Ο / Ο34586

^r 2-Ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-dimethylaminosulfonate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl- (N-methyl-N-acetyl) -aminosulfonate

N-4-chlorophenyl-allylbernsteinsäureamId 2-methyl-4,6-dinitrophenol (salts, esters) of 2-sec-butyl-4,6-dinitrophenol (salts) 2-sec-butyl-4-dinitrophenol _J 6 ^ acetate 2- tert-butyl-4,6-dinitrophenol acetate

2-tert-butyl-4,6-dinitrophenol (salts) ^ -t-Butyl-S-methyl ^ jS-dinitrophenol (salts) 2-tert-butyl-5-methyl-4-dinitrophenol _J 6-acetate

2-sec. Amyl-4,6-dinitrophenol (salts, esters) 1- (μC -dimethylbenzyl) -3- (4-methylphenyl) -harnst of f l -phenyl-3- (2-methylcyclohexyl) -urea l -Phenyl-1-benzoyl-3,3-dimethyl-urea 1- (4-chlorophenyl) -l-benzoyl-3,3-dimethyl-urea 1- (4-chloro-phenyl) -3,3-dimethyl-urea 1 - (4-Chloro-phenyl) -3-methyl-3-butyn-1-yl-3-urea 1- (3,4-dichlorophenyl) -3,3-dimethyl-urea 1- (3,4-chloro-phenyl) -l- benzoyl-3,3-dimethyl-urea 1- (3,4-dichlorophenyl) -3-methyl-3-n-butyl-urea 1- (4-i-propylphenyl) -3,3-dimethyl-urea 1- ( 3-trifluoromethylphenyl) -3,3-dimethyl-urea 1- (3-i, u <1, ß, ß-tetrafluoroethoxyphenyl) -3,3-dimethyl-urea.

l -. (3-tert-butylcarbamoyloxy-phenyl) -3,3-dimethyl-urea

1- (3-Chloro-4-ethylphenyl) -3,3-dimethyl-urethane tert-3- (3-chloro-4-methoxyphenyl) -3,3-dimethyl-urea 1- (3,5-dichloro-4 methoxyphenyl) -3,3-dimethyl-urea

232125 1

- 49 - ° · ² · 0050/034586

1- [4 (1-chloro-phenoxy) -phenyl] -3,3-dimethyl-urea 1- [4 (4'-methoxy-phenoxy) -phenyl] -3,3-dimethyl-urea

l-Cyclpoctyl-3,3-dlmethy1-urea

1- (hexahydro-4,7-methanindan-5-yl) -3,3-dimethyl-urea-5 material

1- [1- or 2- (3a, 4 _J 5,7,7a-hexahydro) -4-7 _J methanoindanyl3-

-3,3-dimethyl-urea

l- (4-Pluorphenyl) -3-carboxymethoxy-3-methy1-urea

l-phenyl-S-methyl-S-inethoxy-urea l- (4-chlorophenyl) -3-methyl-3-methoxy-urea l- (4-bromophenyl) -3-methyl-3-methoxy-urea l- ( 3,4-dichlorophenyl) -3-methyl-3-methoxy-urea

1- (3-chloro-4-broinophenyl) -3-methyl-3-methoxy-urea f

1- (3-Chloro-4-isopropyl-phenyl) -3-methyl-3-methoxy-urea 15- (3-chloro-4-methoxyphenyl) -3-methyl-3-niethoxy-urea 1- (3-tert. Butyl phenyl) -3-methyl-3-niethoxy-urethane

1- (2-Benzothiazolyl) -1,3-dimethyl-urea 1- (2-benzthiazolyl) -3-methyl-urea

material

Imidazolldin-2-on-l-carboxylic acid iso-butyl amide

_1J 2-Dimethyl-3> 5-diphenylpyrazolium methylsulfate W 'l, 2 _J 4-trimethyl-3,5-diphenylpyrazolium methylsulfate

1,2-Dimethyl-4-bromo-3j5-diphenylpyrazolium methylsulfate 25 l, 3-Dimethyl-4- (3 _J 4-dichlorobenzoyl) -5 - [(4-methylphenyl) -

sulfonyl-oxy] -pyrazole 2,3,5-trichloropyridinol- (4)

l-methyl-3-phenyl-5- (3'-trifluoromethylphenyl) -pyridon- (4)

1-Methyl-4-phenyl-pyridinium chloride 1,1-dimethylpyridine-methanol-chloride 3-phenyl-4-hydroxy-6-chloropyridazine 1, 1'-dimethyl-4,4'-dipyridyl-di-di (methylsulfate)

l, l'-di (3,5-dimethyl-morpholine-carbonylmethyl) -4,4-di-

pyridylium dichloride l, l ^f -Ethylene-2,2 ^f -dipyridylium dibromicl

232125 1

- 50 - 0 · Ζ. ΟΟ5Ο / Ο34586

* "3-Cl (N-ethoxyamino) -propylidene] -6-ethyl-3,4-dihydro-2-H-pyrene-2,4-dione

3-Cl- (N-Allyloxyamino) -propylidene] -6-ethyl-3,4-dihydro-

-2-H-pyran-2,4-dione 5 2- [1- (N-allyloxyamino) -propylidene] -5,5-dimethylcyclohexylamine

-1,3-dione (salts)

2-Cl- (N-AlIyloxyamino) butylidene] -5,5-dimethylcyclohexan-

-1,3-dione (salts) '

2-Cl- (N -allyloxyamino) butylidene] -5,5-dimethyl-4-methoxy-10-carbonyl-cyclohexane-1j-dione (salts)

2-chlorophenoxyacetic acid (salts, esters, amides) 4-chlorophenoxyacetic acid (salts, esters, amides) 2,4-dichlorophenoxyacetic acid (salts, esters, amides) 2,4,5-trichlorophenoxyacetic acid (salts, esters, amides) 2-methyl 4-chlorophenoxyacetic acid (salts, esters, amides) "3,5" 6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides)

^ Chloro-il-trifluoromethyl-S-ethoxycarbonyl-4'-nitrophenyl

ether

1- (4-Benzyloxyphenyl) -3-methyl-3-methoxyurea 2-Cl- (2,5-dimethylphenyl) -ethylsulfonyl] -pyridine-N-oxide 1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole 3-Anilino-4-methoxycarbonyl-5-methylpyrazole 3-tert-butylamino-4-methoxycarbonyl-5-methylpyrazole N-Benzyl-N-isopropyltrimethylacetamide

2-C4- (4'-chlorophenoxymethyl) -phenoxy] -propionic acid methyl->; ester

2-C4- (5-bromopyridyl-2-oxy) phenoxy] -propionsäuremethyl-

ester

2-C4- (5'-Jodpyridyl-2-oxy) phenoxy] propionate

2- C4- (5'-iodopyridyl-2-oxy) -phenoxy! -Propionic acid - !!, butyl ester

IL I I

- 51 - ° · ² · ΟΟ5Ο / Ο34586

^ 2-chloro-4-trifluoromethylphenyl-3 '- (2-fluoroethoxy) -4'-nitro-phenyl ether

2-chloro-4-trifluoromethylphenyl-3- (ethoxycarbonyl) methylthio-4-nitrophenyl ether

2,4,6-trichlorophenyl-3 (ethoxycarbonyl) methylthio-4-nitro-phenyl ether

2- [1- (N-ethoxaaino) -butylidene] -5- (2-ethylthiopropyl) -3-hydroxycyclohexene (2) -one- (l) (salts)

2- [1- (N -ethoxamino) -butylidene] -5- (2-phenylthiopropyl) -3-hy-K) -hydroxy-cyclohexene (2) -one- (l) (salts)

4- [4- (4'-trifluoromethyl-phenoxy-pentene-S-carboxylic acid

ethyl ester

2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrophenyl ether

2,4-dichlorophenyl-3'-carboxy-4'-nitrophenyl ether (salts). 4,5-Dimethoxy-2- (3-C, _J- β-trifluoro-β-bromonethoxyphenyl) -3- (2H) -

-pyridazinone

2,4-dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl ether

2,3-dihydro-3,3-dimethyl-5-benzofuranyl ethanesulfonate N- [4-methoxy-6-methyl-l _J 3,5-triazin-2-yl-aminocarbonyl] -

-2-chloro-benzenesulfonamide

l (3-chloro-4-ethoxyphenyl) -3,3-dimethylurea 25 2-Methyl-4-chlorophenoxy-thioacetic acid ethyl ester 2-chloro-3 _J 5-di-iodo-4-acetoxy-pyridine

l (-4- [2- (4-methylphenyl) -ethoxy] phenyl-3-methyl-3-methoxy-

urea

_4J 5-dimethoxy-2- (3 - ^, ^, ß-trifluoro-ß-br ^> omethoxyphenyl) -3-

- (2H) -pyridazinone

2,4-dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl

ethers

2,3-dihydro-3,3-dimethyl-5-benzofuranylethanesulfonate N-r4-methoxy-6-methyl-1 _J 3 _J 5-triazine-2-yl-aminocarbonyl] -

232125 1

· * '- '" ^r - 52 - OZ OO5O / O34586

-2-chlorobenzenesulfonamide l (3-chloro-4-ethoxyphenyl) -3,3-dimethylurea 2-Methyl-4-chlorophenoxy-thioacetic acid ethyl ester 2-Chloro-3,5-diiodo-4-acetoxy-pyridine

l- (4 ~ [2- (4-methylphenyl) -ethoxy] phenyl) -3-methyl-3-methoxyurea

In addition, it is useful to add the new compounds alone or in combination with other herbicides

K) mixed other pesticides together, for example, with agents for controlling pests or phytopathogenic fungi or .Bakterien. Also of interest is the miscibility with mineral salt solutions, which are used to eliminate nutrient or trace

15 element defects are used. Non-phytotoxic oils and oil concentrates may also be added.

When testing for selective herbicidal action in Nachauflauf application in a greenhouse at application rates of 2.0 kg / ha, the new compound 2 shows a better selective herbicidal activity than the known drug A.

Likewise, the active ingredient No. 3 in the selective weed control in postemergence in the greenhouse at application rates of 1.0 kg total active ingredient / ha a better selective herbicidal activity than the known drug 3 in the same application rate calculated on acid basis.

When testing the herbicidal action in pre- and post-emergence treatment in a greenhouse at application rates of 3 kg / ha total active ingredient, the new compounds No. 6, 8, 11, 22 and 56 show a fairly good herbicidal activity.

23 212 5 1

- 53 - ° · ² - 0050/03 ^ 586

In further experiments with post-emergence in the greenhouse, the compounds no. 27 and no. 25 at 1.0 kg / ha showed a very good or acceptable compatibility for the crop rice. At the same time, broad-leaved undesirable plants were sensitively damaged. Crucial for this is the very good compatibility of the compounds for a crop from the Gramineae family.

O ¹⁰

25

30

35

ul

Table 1 List of plant names

Botanical name

Abbreviation in table

German name

English name

Arachys hypogaea Arachys hyp. - peanuts ι Chenopodium album - White goosefoot lambsquarters VJl J = Galium aparine - Catchweed, burdock lab herb catchweed bed straw I Hordeum vulgar Hordeum vulg. barley barley Ipomoea spp. - Morning glory species morning glory Sinapis alba - " White mustard white mustard Triticum aestlvum Tritic. aest. wheat wheat Amaranthus retroflexus - curved back foxtail redroot pigweed Matricaria spp.   - chamomile species chamomile Oryza sativa rice rice

ro στ

O O Ui O

O U)

J = - VJi

Claims (1)

232125 1 - 55 - ° · ^ζ · 0050/034586 invention claim Herbicidal agent, characterized by a content of a solid or liquid carrier and a 2-fluoroalkanecarboxylic acid compound of the general formula R ² R ³ TO F ^ ^R wherein R is an optionally substituted aryl or heteroaryl aryl radical, 2 "3 R and R are independently hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl radical, X is oxygen or sulfur and t s Il cc a hydroxyl group or the groups OR, SR or ^X ^ J mean, in which c
R is an optionally substituted alkyl, alkenyl, Alkynyl, cycloalkyl, cycloalkenyl, alkanone, Aryl, heteroaryl or heteroarylalkyl, R is hydrogen or the radicals mentioned for R except an optionally substituted m-anilino radical, 7 6 5 R is independently of R the radicals mentioned for R or a hydroxyl group or an optionally substituted alkoxy or alkylthio radical, a cyano or 232125 1 - 56 - 0.2. 0050/034586 Cyanoalkyl group or the remainder N means \ 9 8 Q 5 wherein R and R "are independently hydrogen or an optionally substituted alkyl or aryl radical C year and further R and R 'together with the adjacent nitrogen atom represent an optionally substituted heterocyclic radical which optionally contains one or more double bonds or in addition to the nitrogen atom contains one or more heteroatoms, or the salts of this compound.