CS251778B2 - Herbicidal composition and method for producing active ingredients - Google Patents

Abstract

Herbicidal composition, especially for controlling weeds in crops of useful plants, characterized in that, in addition to carriers and/or other additives, it contains as an active ingredient at least one 2-phenoxypropionic acid cyanamide of the general formula I O-CH-CO-N I CH3 R (i). CN

Description

The present invention relates to a herbicidal composition which contains as an active ingredient novel herbicidally active 2-phenoxypropionic acid cyanamides. Furthermore, the invention relates to a process for producing these novel herbicidally active 2-phenoxypropionic acid cyanamides and their use for selectively controlling weeds in crops.

The 2-phenoxypropionic acid cyanamides according to the invention correspond to the general formula I

T-0——O-CH-CO-N-R (I)

CH,

CN in which

R represents a hydrogen atom, an alkyl group with 1 to 3 to 4 carbon atoms or an alkoxyalkyl group with 2 to 4 carbon atoms, an alkenyl group with 2 to 4 carbon atoms and

T stands for a group of the general formula

in which

X represents a fluorine, chlorine, bromine or trifluoromethyl group, Y represents a hydrogen, fluorine or chlorine atom,

Z represents a nitrogen atom or a methine bridge.

Herbicidally active 2-phenoxypropionic acid amides with further substituents in the p-position of the phenyl ring are known from the literature, such as from German Patent Application Nos. 2,433,067, 2,531,643, 2,639,796, 2,640,730 or 3,004,770.

It has now been surprisingly found that the new active ingredients according to the present invention are superior in their effect to the compounds of this group of compounds described in the literature in the selective control of weeds in crops of useful plants.

Within the scope of the present invention, the following substituents fall within the scope of the symbols used in defining general formula I, for example:

R generally represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, all four isomers of the butyl group, an allyl group, a methylyl group, a 2-butenyl group, a 3-butenyl group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, as well as an ethoxyethyl group,

T generally represents a radical substituted by at least one radical X from the group consisting of phenyl, 2-pyridinyl, 2-quinolinyl, 2-quinoxalinyl, 2-quinoxalinyl, 2-benzoxazolyl or 2-benzothiazolyl.

The symbol R preferably represents a hydrogen atom or a saturated group, such as an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 4 carbon atoms, and the symbol T preferably represents a 2-benzoxazolyl group or a 2-quinoxalinyl group.

Due to their good selective herbicidal effect, preferred compounds of the general formula I are those compounds in which bu3

and)

b)

R represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms or T represents a group of the formula

or

C)

T stands for the formula group

or

d) T means a group of the formula

Within subgroup a), those compounds in which R represents an alkyl group with 1 to 4 carbon atoms are preferred.

Within subgroup b) those compounds are preferred in which bu3 X represents a trifluoromethyl group, Y represents a hydrogen atom and Z represents a methine bridge; or X represents a trifluoromethyl group, Y represents a hydrogen atom and Z represents a nitrogen atom; or X and Y represent chlorine and

Z represents a nitrogen atom; or X represents chlorine, Y represents fluorine and Z represents nitrogen; i.e. T represents a group selected from the group consisting of 4-trifluoromethylphenyl, 5-trifluoromethylpyridin-2-yl, 3,5-dichloropyridin-2-yl and 5-chloro-3-fluoropyridin-2-yl.

Within subgroup o), those compounds in which X represents fluorine or chlorine are preferred.

Very particularly preferred subgroups of compounds of the general formula I are characterized in that

R represents an alkyl group with 1 to 4 carbon atoms and T represents either a 4-trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group or a 3,5-dichloropyridin-2-yl group or a 5-chloro-3-fluoropyridin-2-yl group, the latter type being suitable, further in that R represents an alkyl group with 1 to 4 carbon atoms and T represents a 6-fluoroquinoxalin-2-yl group or a 6-chloroquinoxalin-2-yl group, or R represents an alkyl group with 1 to 5 carbon atoms and T represents a 6-chlorobenzoxazol-2-yl group.

Preferred individual compounds include:

N-cyano-N-methylamide of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid, N-cyano-N-methylamide of 2-[4-(5-trifluoromethylpyridin-2-yloxy)phenoxypropionic acid,

N-cyano-N-ethylamide 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid, N-cyano-N-ethylamide 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]propionic acid, N-cyano-N-methylamide 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]propionic acid, N-cyano-N-ethylamide 2-[4-(6-fluoroquinoxalin-2-yloxy)-phenoxy]propionic acid, N-cyano-N-methylamide 2-[4-(6-fluoroquinoxalin-2-yloxy)-phenoxy]propionic acid or N-cyano-N-n-butylamide 2-([(6-chlorobenzoxazol-2-yloxy> phenoxy]propionic acid.

Compounds of general formula I can be prepared according to the present invention by reacting a 2-phenoxypropionic acid halide of general formula II τ-ο-^θ0—CH—CO—Hal I ch ₃ in which

T is as defined under formula I and Hal is chlorine or bromine, acting in the presence of a cyanamine acid binding agent of formula III

CN in which

R is given under formula I.

In addition to the process according to the invention, the active compounds of the general formula I can also be prepared according to other processes.

In the case where R has a different ... than a hydrogen atom, the compounds of general formula Ia can be

T-0-^)—

0—CH—CO—N—R (la) in which

T has the meaning given under formula Ia

R·'· represents an alkyl group with 1 to 4 carbon atoms, an alkenyl group with 3 to 4 carbon atoms or an alkoxyalkyl group with 2 to 4 carbon atoms, obtained by reacting the corresponding cyanoamino derivative of the general formula lb

T-0

-CH-CO-N-H

I I

CH ₃ CN in which

T has the meaning given under formula I, acts in the presence of an acid-binding agent with a halogen derivative of general formula IV

Hal - R ¹ < IV ) in which

R ¹ has the meaning given under the formula 1a and Hal means chlorine, bromine or iodine.

According to another process, the compounds of general formula I as mentioned and defined above can also be obtained by reacting a phenoxypropionic acid derivative of general formula V

HIM

ch ₃

O-CH-C-N-R (V) in which

CN

R has the meaning given under formula I, acting in the presence of an acid-binding agent with a halide of general formula VI

T - Hal (VI) in which

T has the meaning given under the formula Ia Hal is fluorine, chlorine, bromine or iodine.

According to another process, the compounds of general formula I as mentioned and defined above can be obtained by reacting a propionic acid derivative of general formula VII

Hall

CH-π

I ³ β

CH - C jviij’ ch in which

R has the meaning given under formula la

Hal represents chlorine, bromine, tosyl group or mesyl group, acts in the presence of an acid-binding agent with a hydroquinone derivative of general formula VIII

T-0

OH (VIII) in which

T has the meaning given under Formula I.

The various reactions leading to the compounds of the general formula I, or la from the compound of the formula lb, can be carried out preferably in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably between -20 and +120 °C. Tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo2,2,2-octane, 1,5-diazabicyclo 4,3,0 non-5-ene or 1,8-diazabicyclo 5,4,0, undec-7-ene are particularly suitable as bases. However, inorganic bases such as hydrides, for example sodium hydride or calcium hydride, hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate or bicarbonates such as potassium bicarbonate or sodium bicarbonate can also be used as bases.

The intermediates of the general formulas II, III, IV, VI and VIII are for the most part known compounds or can be prepared analogously according to known procedures.

The intermediates of general formulas V and VII are novel and have been specifically prepared for the synthesis of compounds of general formula V.

Propionate derivative I.

acids of general formula VII ? ^H 3 OI li

Hal -CH-C-N-R

AND

CN (VII) in which

R and Hal have the meanings given above in general formula IX, is obtained by reacting the propionic acid halide

CH

Hal - CH - C - Hal

ÍIX) in which

Hal has the meaning given under formula VII a

Hal'*' means chlorine or bromine, reacts in the presence of an acid-binding agent with a cyanamine of formula X

H - jJ - R CN (X) in nemz *R has the meaning given by formula VII.

According to a variant of the above process, it is also possible to first prepare compounds of general formula VIIa

Hall

CH.

I ³

CH ·

NH

CN (Villa)

Ί •251778 in which

Hal has the meaning given above, in that IX is first treated with cyanamide of formula XI in the presence of a reagent that binds the acid.

H ₂ N - CN (XI) and the obtained compounds of general formula VIIa are optionally treated with an alkylating agent, introducing a radical as defined under formula IV.

Intermediates of the above formula V can be prepared from compounds of the general formula VII by reacting a compound of the general formula VII with

CK ₃ (VII)

Hal - CH - C - N - R

AND

CN in which

Hal and R have the meanings given above, act in the presence of a base with 4-benzyloxyphenol and the obtained compound of general formula XII

ch _{3 o} I ii

O-CH — C-N-R

CN (XII) in which

R has the meaning given under formula I, is treated with hydrogen in the presence of a hydrogenation catalyst, such as for example on coal.

The starting materials of the general formulae IX, X or XI are known or can be prepared according to known methods. The novel intermediates of the general formula XII have been specifically designed and prepared for the synthesis of the compounds of the general formula I.

The new intermediates of general formulas V and VII are prepared by methods known per se. The reaction conditions are always chosen according to the reactants used.

The new process makes it possible to produce compounds of general formula Ic

F

(Ic)· in which

R and X have the meanings given under formula I, whereby (XXII),

a) 3-nitropyridine of general formula XIII / x no ₂

Har in which

X has the meaning given under formulas I and 2

Hal represents fluorine, chlorine or bromine, is reacted in the presence of a base with hydroquinone to form a compound of general formula XIV

NO,

Olympic Games (XIV), in which

X has the meaning given under formula I, this intermediate is reduced in the presence of a metal catalyst to the amino compound of general formula XV

X / ^NH 2 in which —OH (XVI),

X has the meaning given under formula I, this compound is diazotized and by the action of a fluorinating agent it is converted into a compound of general formula XVI in which

OH (XVI) ,

X has the meaning given under formula I, and in the presence of a base with a propionic acid derivative or by reacting this fluorinated intermediate with an acid of general formula VII,

b) nitropyridine of general formula XIII is reacted in the presence of a base with a propionic acid ester of general formula XVII

CH,

AND

O-CH — COO-alkyl (XVII), in which

alkyl means an alkyl group with 1 to 4 carbon atoms, the intermediate obtained of general formula XVIII

(XVIII) in which

X and alkyl have the meanings given above, is reduced in the presence of a metal catalyst to an amino compound of the general formula XIX

CH,

I ³

O-CH-COO-alkyl (XIX) in which

X and alkyl have the meanings given above, the amino compound is diazotized and the diazotized product is treated with a fluorinating agent to form a compound of the general formula XX

F f ^H 3 •°—/Λ— O-CH-COO-alkyl (XX) , in which

X and alkyl have the meanings given above, this ester is saponified and converted by the action of a halogenating agent into a 2-phenoxypropionic acid halide of the general formula Ha

F

in which

Hal and X have the meanings given under formula II, and in the presence of a base it is reacted with a cyanamine of general formula III.

According to one variant of the above process, the intermediates of general formula XVIII can also be obtained by treating compounds of general formula XIV in the presence of a base with a propionic acid ester of general formula XXI ^CH 3 . (XXI)

Hal - CH - C00 - alkyl in which

Hal represents chlorine or bromine and alkyl represents an alkyl group having 1 to 4 carbon atoms.

The reaction conditions for the reaction steps known per se, such as catalysts, solvents and reaction temperatures, are known from the literature.

The starting materials of general formulas XIII and XVII are known.

The intermediates of general formulas XIV, XV and XVIII are novel and have been specifically prepared for the synthesis of compounds of general formula Ic.

Also novel are compounds of the general formula IIa in which X represents halogen.

The compounds of formula I occur as racemates. The present invention relates to both enantiomers of the active compounds of formula I as well as to mixtures thereof. Unless a specific isomer is explicitly mentioned, the information given in the description always refers to the racemates.

The active ingredients of formula I are stable compounds. Handling of these compounds does not require any safety precautions.

At very low application rates, the compounds of the formula I are characterized by good selective herbicidal properties, especially against monocotyledonous weeds. Due to these properties, the compounds are excellently suited for use in crops of dicotyledonous useful plants, in particular in cotton, soybeans, rapeseed, sugar beet and fodder beet, as well as in sunflower. In part, the compounds of the formula I according to the invention can also be used as selective herbicides in monocotyledonous cultivated plants, such as cereals, for example wheat and barley. In this case, weeds are also partially controlled, which could only be controlled with total herbicides up to now.

At higher application rates, the compounds of formula I have total herbicidal properties.

The selective herbicidal action of the compounds according to the invention has been found both in pre-emergence and post-emergence applications. These active ingredients can be used with equal success in pre-emergence and post-emergence applications for the selective control of weeds, especially against monocotyledonous weeds.

The present invention also relates to a herbicidal composition, which is characterized in that it contains at least one compound of the general formula I as an active ingredient.

The compositions according to the invention are used to control monocotyledonous weeds, especially grasses, in pre-emergence and post-emergence applications.

The compounds of the formula I are used in unmodified form or preferably in the form of compositions together with the auxiliaries customary in the preparation of such compositions and are therefore processed, for example, into emulsion concentrates, into directly sprayable solutions or into solutions which are further diluted, diluted emulsions, wettable powders, soluble powders, dusts, granules, also encapsulated, for example, in polymeric substances. The application methods such as spraying, misting, dusting, sprinkling or pouring, as well as the type of composition, are selected according to the desired objectives and the given ratios.

The compositions mentioned, i.e. compositions containing the active ingredient of the formula I and optionally a solid or liquid additive, concentrates or application forms are produced in a known manner, for example by thoroughly mixing and/or grinding the active ingredients with diluents, such as solvents, solid carriers and optionally surface-active compounds (surfactants).

Suitable solvents include: aromatic hydrocarbons, preferably fractions with 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, highly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, for example for dusts and dispersible powders, natural flours such as limestone, talc, kaolin, montmorillonite or attapulgite are usually used.

Highly dispersed silicic acid or highly dispersed absorbent polymers may also be added to improve physical properties.

Porous types such as pumice, brick dust, sepiolite or bentonite are suitable as granulated adsorptive carriers; non-sorptive carriers such as limestone or sand are suitable. In addition, a wide range of pre-granulated materials of inorganic or organic origin can be used, such as dolomite or ground plant residues.

Suitable surface-active compounds, depending on the type of use of the active ingredient of the formula I, are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants also include surfactant mixtures.

Preferred anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

Soaps include salts of higher fatty acids (with 10 to 22 atoms) with alkali metals, alkaline earth metals or optionally substituted amine salts, such as sodium or potassium salts of oleic acid or stearic acid, or mixtures of natural fatty acids, which are obtained, for example, from coconut oil or tallow. Mixtures of methyltaurine with fatty acids should also be mentioned.

However, so-called synthetic surfactants are more often used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fatty sulfonates or sulfates are generally present in the form of alkali metal salts, alkaline earth metal salts or in the form of optionally substituted ammonium salts and contain an alkyl radical with 8 to 22 carbon atoms, the alkyl radical also being able to include the alkyl part of radicals such as, for example, the sodium or calcium salt of lignisulfonic acid, the ester of dodecyl sulfuric acid or mixtures of sulfated fatty alcohols which have been produced from natural fatty acids.

This also includes salts of sulfuric acid esters and sulfonic acids with adducts of fatty alcohols with ethylene oxide. Sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid residues and a fatty acid residue with 8 to 22 carbon atoms. Alkylaryl sulfonates are represented, for example, by the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and formaldehyde.

Corresponding phosphates, such as salts of the phosphoric acid ester of the adduct of 4 to 14 mol of ethylene oxide with p-nonylphenol, or phospholipids, are also suitable.

Non-inogenic surfactants include, in particular, derivatives of polyglycol ethers of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the alkyl residue of alkylphenols.

Other suitable non-inogenic surfactants are water-soluble adducts of polyethylene oxide with propylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Furthermore, esters of polyoxyethylene sorbitan with fatty acids, such as polyoxyethylene sorbitan trioleate, are also suitable.

Cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical with 8 to 22 carbon atoms as substituents on the nitrogen atom and contain lower or halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. These salts are preferably present in the form of halides, methyl sulfates or ethyl sulfates, such as stearyltrimethylammonium chloride or benzyl-di-(2-chloroethyl)ethylammonium bromide.

Surfactants commonly used in the preparation of such compositions are described, among others, in the following publications: Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ringwood, New Jersey, 1981. H. Stache, Tensid-Tauschenbuch, 2nd Edition, C. Hanser Verlag, Munich,

Vienna, 1981.

M. and J. Ash. Encyclopedia og Surfactants, Vol. 1/III, Chemical Publishing Co., New York, 1980-1981.

Active ingredient compositions generally contain 0.1 to 95% by weight of the active ingredient of the formula X, in particular 0.1 to 80% by weight of the active ingredient of the formula I, 1 to 99.9% by weight of solid or liquid additives and 0 to 25% by weight, in particular 0.1 to 25% by weight of surfactants.

Preferred compositions have in particular the following composition (4 = % by weight):

Emulsifiable concentrates:

active ingredient surfactant liquid carrier

Ask:

active substance solid carrier substance

Suspension concentrate:

active ingredient water surfactant

Wettable powder:

active ingredient surfactant solid carrier

Granulate:

active substance solid carrier substance

1 until 20 4, advantageously 5 . until 10 4 5 until 30 4, advantageously 10 until 20 4 50 until 94 4, advantageously 70 until 85 4

0.1 to 10 4, preferably 0.1 to 1% 99.9 to 90 4, preferably 99.9 to 99%

5 until 75 4, advantageously 10 to 50% 94 until 25 4, advantageously 90 to 30% 1 until 40 4, advantageously 2 to 30 4

0.5 to 90%, preferably 1 to 80%

0.5 to 20 4, preferably 1 to 15% 5 to 95 4, preferably 15 to 90 4

0.5 to 30 4, preferably 3 to 15% 99.9 to 70 4, preferably 97 to 85 4.

While concentrated products are preferred as commercial products, the end consumer usually uses diluted products. Application forms can be diluted down to a content of 0.0014 of active ingredient.

The application rate is generally 0.01 to 10 kg of active ingredient/ha, preferably 0.025 to 5 kg of active ingredient per 1 ha.

These compositions may also contain other additives, such as stabilizers, antifoaming agents, viscosity regulators, binders, adhesives, as well as fertilizers or other active substances to achieve special effects.

The following examples illustrate the invention in more detail, but do not limit its scope in any way.

Examples illustrating the method of production of active ingredients:

Example Hl

2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid N-cyanamide (compound No. 1.4),

127°C.

10.4 g (0.1575 mol) of 85% potassium hydroxide are dissolved in 75 ml of water. At 20 °C, 3.5 g (0.0825 mol) of cyanamide are added and the clear, colorless solution is cooled to 10 °C. A solution of 25.8 g (0.075 mol) of 2-[4-(4-trifluoromethylphenoxy,-phenoxy]propionic acid chloride in 15 ml of acetone is then added dropwise so that the temperature does not exceed 15 °C. The reaction mixture is then stirred for 45 minutes at this temperature and then 9 g (0.09 mol) of 37% aqueous hydrochloric acid are added dropwise at 5 °C. The product is separated in oily form, but crystallizes on standing within 30 minutes.

The colorless crystals are filtered off and washed with water. After drying with phosphorus pentoxide, 24.9 g (95.0% of theory) of 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid N-cyanamide are obtained, melting point 125-127°C.

Example H2

2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid N-cyano-N-methylamide (compound no. 1.3)

17.5 g (0.05 mol) of 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid N-cyanamide are dissolved in 60 ml of methyl ethyl ketone and the solution is heated under reflux together with 7.6 g (0.055 mol) of potassium carbonate for 30 minutes. 3.6 ml (0.057 mol) of methyl iodide are then added to the colorless suspension at 30 °C and the mixture is stirred for a further 2 hours at the same temperature. The reaction mixture is now filtered and the filtrate is evaporated. The oily residue is chromatographed on silica gel using a 3:1 mixture of petroleum ether and ethyl acetate as eluent. Evaporation of the main fraction gives 10.9 g (59.9% of theory) of N-cyano-N-methylamide

2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid in the form of a colorless clear oil 23 and refractive index ηθ =1.5228.

Example H3

2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionic acid N-cyano-N-butylamide (compound no. 2.4)

O-CH-CO-N-CH ₂ -CH ₂ CH ₂ CH ₃ ch ₃ CN

a) 2-Bromopropionic acid N-cyano-N-methylamide

10.5 g (0.25 mol) of cyanamide are dissolved in 250 ml of 2N potassium hydroxide solution and the solution is cooled to +10 °C. At this temperature, 26.5 ml (0.25 mol) of 2-bromopropionic acid bromide are added dropwise and the reaction mixture is stirred for 1 hour at the same temperature. Then 16.8 g (0.2 mol) of sodium bicarbonate are added. At a temperature of 20 °C, 63 g (0.5 mol) of dimethyl sulfate are then added dropwise. The reaction mixture is stirred for 4 hours and then the reaction mixture is extracted with methylene chloride. The combined organic phases are dried over sodium sulfate and evaporated. The residue is obtained

27.5 g of crude product. From this crude product, 13.6 g (28.5% of theory) of 2-bromopropionic acid N-cyano-N-methylamide with a boiling point of 45 to 47 °C/0.8 Pa are obtained by vacuum distillation.

b) 2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-methylamide

To a solution of 20.0 g (0.1 mol) of hydroquinone monobenzyl ether and 16.5 g (0.12 mol) of potassium carbonate in 200 ml of dimethylformamide, 19.1 g (0.1 mol) of 2-bromopropionic acid N-cyano-N-methylamide are added dropwise with vigorous stirring. After the weak exothermic reaction has subsided, the reaction mixture is heated for 3 hours at 40 °C. The salts that have separated are then filtered off and the filtrate is evaporated. The residue is dissolved in ether and dilute sodium hydroxide solution is added to the solution and the mixture is shaken. After drying the organic phase with sodium sulfate, the solvent is evaporated and the residue is distilled in vacuo. 19.5 g (63% of theory) of 2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-methylamide with a melting point of 56 to 58 °C are obtained.

c) 2-(4-hydroxyphenoxy)propionic acid N-cyano-N-butylamide

16.5 g (0.047 mol) of 2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-butylamide, which was prepared analogously to example b), was hydrogenated in 170 ml of dioxane in the presence of 1.7 g of palladium on carbon as a catalyst (5%) with hydrogen. The catalyst was then filtered off and the filtrate was evaporated. Chromatography on silica gel using a 3:1 mixture of ethyl acetate and hexane as eluent gave 7.5 g (61% of theory) of 2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-butylamide.

-hydroxyphenoxy)propionic acid in the form of a colorless oil. n _Q = 1.5132.

d) 4.4 g (0.017 mol) of 2-(hydroxyphenoxy)propionic acid N-cyano-N-butylamide, 3.8 g (0.02 mol) of 2,6-dichlorobenzoxazole and 3.5 g (0.025 mol) of potassium carbonate are stirred in 50 ml of acetonitrile for 10 hours at room temperature. The salts are then filtered off and the filtrate is evaporated. Chromatography on silica gel using a 1:3 mixture of ethyl acetate and hexane gives 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propionic acid N-cyano-N-butylamide, melting point 91-92°C.

Example H4

2-Bromopropionic acid N-cyano-N-butylamide

To 13.4 g (0.137 mol) of butyl cyanamide and 13.8 g (0.137 mol) of triethylamine in 150 ml of ether at a temperature of 15 °C, 29.5 g (0.137 mol) of 2-bromopropionic acid bromide are added dropwise. The reaction mixture is stirred for 3 hours at a temperature of 20 to 25 °C and the salt formed is filtered off, the filtrate is extracted with dilute hydrochloric acid, dried over sodium sulfate and evaporated. The oily residue is distilled under high vacuum. 22.6 g (70.8% of theory) of N-cyano-N-butyl amide of 2-bromo-propionic acid with a boiling point of 53 to 54 °C/0.52 Pa are obtained.

Example H5

2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid N-cyano-N-methylamide (compound no. 1.26)

F

a) 4-(5-chloro-3-nitropyridin-2-yloxy)phenol

A mixture of 85.9 g (0.78 mol) of hydroquinone, 1,200 ml of acetonitrile and 53.9 g (0.39 mol) of potassium carbonate is heated to 60 °C. A solution of 115.8 g (0.60 mol) of 2,5-dichloro-3-nitropyridine in 500 ml of acetonitrile is then added dropwise over 6 hours and the mixture is stirred for a further 36 hours. The solvent is distilled off and the residue is poured into a mixture of ice water and hydrochloric acid. After extraction with methylene chloride, the combined organic phases are dried over magnesium sulphate, clarified with activated charcoal, filtered and concentrated. The residue is purified by crystallization from a mixture of hexane and ethyl acetate. 99 g (62% of theory) of 4-(5-chloro-3-nitropyridin-2-yloxy)phenol with a melting point of 125-126°C are obtained.

b) 4-(3-amino-5-chloropyridin-2-yloxy)phenol·

110.7 g (0.415 mol) of 4-(5-chloro-3-nitropyridin-2-yloxy)phenol are dissolved in 1,200 ml of dioxane and, after adding Raney nickel as a catalyst for 22.0 h, hydrogenated at a temperature of 20 to 25 °C with hydrogen. The catalyst is then filtered off, the solution is concentrated and the residue is stirred with hexane. After filtration and drying, 96.0 g (98% of theory) of 4-(3-amino-5-chloropyridin-2-yloxy)phenol with a melting point of 174 °C are obtained.

c) 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol

To 400 g (20 mol) of the hydrogen fluoride presented is added at a temperature between -8 °C and 0 °C

122.5 g (0.518 mol) of 4-(3-amino-5-chloropyridin-2-yloxy)phenol. Then 37.3 g (0.540 mol) of sodium nitrite are added in portions over one hour. The mixture is stirred for 2 hours at °C and slowly heated in an autoclave to 55 °C. Excess hydrogen fluoride is distilled off, the residue is taken up in 200 ml of methylene chloride, neutralized with ice water and ammonia. After drying and evaporation of the organic phase, 112 g of 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol with a melting point of 97 to 98 °C are obtained.

d) 48. g (0.20 mol) of 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol and 38.2 g (0.20 mol) of 2-bromopropionic acid N-cyano-N-methylamide are dissolved in 400 ml of acetonitrile, 35.9 g (0.26 mol) of potassium carbonate and 0.33 g (0.002 mol) of potassium iodide are added to the solution and the reaction mixture is heated for 13 hours at 80 °C. The precipitate is then separated, the filtrate is evaporated and the residue is taken up in 500 ml of methylene chloride. For purification, activated carbon is added to the solution and the mixture is then filtered through silica gel. The filtrate was evaporated and the residue was crystallized from a mixture of hexane and ethyl acetate, yielding 61 g of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid N-cyano-N-methyl ester.

Example H6

N-n-butyl-N-cyanamide 2-[[4-(5) chloro-3-fluoropyridin-2-yloxy)phenyl]propionic acid (compound no. 1.28)

a) 2-[4-(5-chloro-3-nitropyridin-2-yloxy)-phenoxy]propionic acid methyl ester

38.6 g (0.20 mol) of 2,5-dichloro-3-nitropyridine, 41.2 g (0.21 mol) of 2-(4-hydroxyphenoxy)propionic acid methyl ester, 400 ml of acetonitrile, 35.9 g (0.26 mol) of potassium carbonate and 0.33 g (0.002 mol) of potassium iodide are heated for 13 hours at 80 °C. The reaction mixture is filtered and the filter cake is washed with acetonitrile. The filtrate is evaporated and the residue is taken up in 500 ml of methylene chloride. Then 15 g of activated carbon are added to the solution and the mixture is filtered through silica gel and the filtrate is evaporated. The residue is crystallized from a mixture of hexane and ethyl acetate. 65.7 g (93.1% of theory) of 2-[4-(5-chloro-3-nitropyridin-2-yloxy)phenoxy]propionic acid methyl ester are obtained, melting point 91 to -92°C.

b) 2-[~4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]propionic acid methyl ester

190.8 g (0.541 mol) of methyl 2-(4-(5-chloro-3-nitropyridin-2-yloxylphenoxy)propionic acid ester are dissolved in 1.9 liters of dioxane, then 40 g of Raney nickel as catalyst are added and hydrogenated with hydrogen at a temperature of 20 to 25 °C. The catalyst is then filtered off, the solvent is distilled off and the still warm oily residue is crystallized with stirring in hexane. The precipitate is separated and dried. In this way 167.4 g (96% of theory) of methyl 2-[4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]propionic acid ester with a melting point of 92 to 94 °C are obtained.

c) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid methyl ester

400 g (20 mol) of hydrogen fluoride are introduced and 167.4 g (0.518 mol) of 2-([4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]propionic acid methyl ester are added in portions at a temperature of -8 °C to 0 °C. 37.3 g (0.540 mol) of sodium nitrite are then added within one hour and the mixture is stirred for a further 2 hours, having previously been heated slowly to 55 °C in an autoclave. The excess hydrogen fluoride is then distilled off and the residue is neutralized in a mixture of 200 ml of methylene chloride and ice water with concentrated ammonia. Three times extraction with methylene chloride, washing with water, drying and evaporation of the organic extracts yielded 81.0 g (48% of theory) of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid methyl ester with a melting point of 63-64 °C.

X

d) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid

A mixture of 67.0 g (0.206 mol) of methyl 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid ester, 350 ml of dioxane and 250 ml of 1N sodium hydroxide solution is stirred for 2 hours at 40 °C. The reaction mixture is poured onto a mixture of ice and 150 ml of 2N hydrochloric acid solution and extracted twice with ethyl acetate. The extracts are washed with saturated sodium chloride solution, dried over magnesium sulfate, filtered and evaporated. 63.6 g (99% of theory) are obtained

2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid, melting point 95-97°C.

e) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride

63.6 g of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid are dissolved in 700 ml of toluene. 200 ml of toluene are distilled from this solution. After cooling to 90 ^° C, 1 ml (0.34 mol) of thionyl chloride are added dropwise and the solution is stirred for a further 14 hours at this temperature. The volume is reduced to 200 ml by concentration. The toluene solution of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride obtained is used directly for the next reaction step.

f) A solution of 9.9 g (0.030 mol) of 2-4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride in 30 ml of toluene is added dropwise to a solution of 3.5 g (0.035 mol) of triethylamine and 3.2 g (0.033 mol) of N-butylcyanamine in 40 ml of toluene while cooling with ice. After a reaction time of 5 hours, the precipitate is separated and the filtrate is purified by chromatography on silica gel. Evaporation of the eluate gives N-n-butyl-N-cyanamide of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid in the form of a yellowish oil, nj^ = 1.5482.

Example H7

2R {4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy}propionic acid N-ethyl-N-cyanamide

To a solution of 2.1 g (0.030 mol) of ethylcyanamine and 9.9 g (0.030 mol) of 2R-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride (melting point 47 to 47 °C) in 30 ml of acetonitrile, a solution of 4.43 g (0.030 mol) of 1,8-diazabicyclo[5,4,0 undec-7-ene (97%) in 10 ml of acetonitrile is added dropwise under ice-cooling. After a reaction time of four hours, the reaction mixture is concentrated. The desired N-ethyl-N-cyanamido-2R-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid is obtained by chromatography on silica gel and evaporation of the eluate (solvent mixture: ethyl acetate and hexane mixture 1:1).

Example H8

N-cyano-N-ethylamide of 2-[4-(6-fluoroquinoxalin-2-yloxy)phenoxy]propionic acid (compound no. 3.18) g (0.039 mol) of 4-(6-fluoroquinoxalin-2-yloxy)phenols. 9.6 g (0.047 mol) of N-cyano-N-ethylamide of 2-bromopropionic acid and 8.1 g (0.058 mol) of potassium carbonate are stirred in 100 ml of acetonitrile for 14 hours at room temperature. The precipitated salts are filtered off, and the filtrate is evaporated. The residue is chromatographed on silica gel using a mixture of ethyl acetate and hexane in a ratio of 1:3 as eluent. 7.1 g (48% of theory) of 2-[4-(6-fluoroquinoxalin-2-yloxy)phenoxy]propionic acid N-cyano-N-ethylamide with a melting point of 108-111°C are obtained.

In an analogous manner, the intermediates and compounds of formula I in the following tables are obtained.

Table 1

Compound X Y Z R physical number properties

1.1 ^CF 3 H N CH ₃ 23 ⁿ D ⁼ 1.5210 1.2 ^CF 3 H N H t.t. 137 - 138 °C 1.3 ^CF 3 H CH ^CH 3 23 ⁿ D = 1.5228 1.4 ^CF 3 H CH H t.t. 125 - 127 °C 1.5 Cl Cl N CK ₃ t.t. 89 - 90 °C 1.6 Cl Cl N H ^23_nD 1.5574

Compound number X Y From R 1.7 Cl . Cl N ^{C2H5 ​} 1.8 Cl Cl N C ₄ H ₉ -n 1.9 Cl Cl N -CH ₂ -CH=CH ₂ 1.10 Cl Cl N - ₍ ch ₂ ) ₂ -oh ₃ 1.11 ^CF 3 H N ^{C2H5 ​} 1.12 ^CF 3 H N C ₄ Hg-n 1.13 ^CF 3 H N -ch ₂ -ch=ch ₂ 1.14 cf ₃ H N -(ch ₂ ) ₂ -och ₃ 1.15 CF ₃ H CH ^{C2H5 ​} 1.16 ^CF 3 H CH ^{C4H9 ​} 1.17 cf ₃ H CH ' -CH ₂ -CH=CH ₂ 1.18 ^CF 3 H N -<CH ₂ ) ₂ -OCH ₃ Compound number X Y From R

physical properties

mp 50 to 55 °C

1.19 cf ₃ Cl N H 1.20 cf ₃ Cl N ch ₃ 1.21 CF ₃ Cl N ^{C2H5 ​} 1.22 cf ₃ Cl N C ₄ H _g -n 1.23 CF ₃ Cl N -CH ₂ -CH=CH ₂ 1.24 ^CF 3 Cl N -(CH ₂ ) ₂ -OCH 1.25 Cl F N H 1.26 Cl F N CH ₃ 1.27 hey F N ^{C2H5 ​} 1.28 Cl F N C ₄ H ₉ -n 1.29 Cl F N -CH ₂ -CH=CH ₂ 1.30 Cl F N -(CH,) -OCH

lip = 1.5122

mp 79 to 80 °C physical properties

tt 93 to 94 °C tt 94 to 95 °C n^ ⁵ = 1.5180 n^ ¹ = 1.5162 n£ ⁵ = 1.5545 n^ ⁵ = 1.5482

Table 2

ch ₃ cn

X

Compound No. X R physical properties 2.1 Cl H 2.2 Cl CH ₃ 2.3 Cl ^{C2H5 ​} 2.4 Cl C ₄ H ₉ -n mp 91 to 92 °C 2.5 Cl -CH ₂ -CH=CH ₂ 2.6 CL - (CH ₂ ) ₂ -OCH ₃ 2.14 F H Compound No. X R physical properties 2.15 F ^CH 3 2.18 CF ₃ H 2.19 cf ₃ CH ₃

Table 3

X X CH, 1 »—OCHCON-R CN Compound No. X R physical properties 3.1 Cl H mp 152 to 154 °C 3.2 Cl CH ₃ mp 106 to 108 °C 3.3 Cl ^{C2H5 ​} mp 106 to 111 °C Compound No. X R physical properties 3.4 Cl C ₄ H ₉ -n mp 62 to 65 °C 3.5 Cl -CH ₂ -CH=CH ₂ 3.6 Cl -<ch ₂ ) ₂ -och ₃ ⁿ⁴⁰ = 1.5794 3.13 F H mp 167 to 169 °C 3.14 F ch ₃ mp 141 to 143 °C 3.17 F C ₄ H ₉ -n mp 94 to 95 °C 3.18 F ^{C2H5 ​} mp 108 to 111 °C

Table 4

Hall

CH,

AND

CH-CO

C - R

AND

CN

Compound number

Hal physical properties

4.1 Br H 4.2 Br CH ₃ t.v. 45 until 47°C/0.8Pa 4.3 Cl H 4.4 Cl ^CH 3 4.5 Cl C ₄ H _g -n 4.6 Br ^C 4 ^H g- ⁿ t.v. 53 until 54°C/0.52Pa 4.7 Br ^{C2H5 ​} t.v. 40 until 45°C/0.75Pa 4.8 Br -(CH ₂ > ₂ OCH ₃ t.v. 85 °C/2 Pa

Table 5 ch ₃

O-CH-CO-N-R

CN

Compound number E R physical properties 5.1 benzyl H 5.2 benzyl CH ₃ mp 56 to 58 °C 5.3 benzyl ^{C2H5 ​} mp 57 to 63 °C 5.4 benzyl C ₄ H ₉ -n mp 108 to 109 °C 5.5 H H . 5.6 H CH ₃ oil 5.7 H ^{C2H5 ​} 5.8 H ^c 4H ₉ -n ηθ ⁵ = 1.5132 Table 6 no ₂ ΎΊί ch ₃ In o—Q-0 1 -CH-COOalkyl Compound number X alkyl physical properties 6.1 Cl ch ₃ mp 91 to 92 °C 6.2 Br ch ₃ 6.3 F ch ₃ 6.4 Cl ^{C2H5 ​} 6.5 Cl C ₄ H ₉ -n 6.6 CF ₃ ch ₃ 6.7 CF ₃ W

Table 7

CH,

AND

O-CH-COOalkyl

Compound number X alkyl physical properties 7.1 Cl CH ₃ mp 92 to 94 °C 7.2 Br ch ₃ 7.3 F ^CH 3 7.4 Cl ^{C2H5 ​} 7.5 Cl C ₄ H ₉ -n oil 7.6 ^CF 3 ^Goal 3 7.7 ^CF 3 C ₄ H ₉ -n

Table 8

O-CH-CO-Q ch ₃

Compound number X Q physical properties 8.1 Cl OH mp 95 to 97 °C 8.2 Cl HER 8.3 Cl OK 8.4 Br OH 8.5 F OH 8.6 ^CF 3 OH 8.7 Cl Cl oil 8.8 Cl Br Compound number X Q physical properties 8.9 Cl F 8.10 Br Cl 8.11 F Cl 8.12 ^CF 3 Cl

2.2

Table 9 compound number X

9.1

9.2

9.3

9.4

Cl

Br

F

Table 10

Compound number X

10.1 Cl

10.2 Br

X

OH physical properties

mp 125 to 126 °C

OH physical properties mp 174 °C

10.3 F

10.4 CF ₃

Table ¹ 11

OH

Compound number X physical properties

11.1 Cl mp 97 to 98 °C

11.2 Br

11.3 F

11.4 CF ₃

Examples illustrating the composition and preparation of the products:

Example Fl

Examples illustrating the composition and preparation of compositions for liquid active ingredients of formula I (%=%) by weight)

25177

a) Emulsion concentrates a) b) c) active substance 20% 40 4 50 % calcium salt of dodexylbenzene- sulfonic acids 5% 8 4 5 .8% polyethylene glycol ether ricin- oil (36 moles of ethylene oxide) 5% - - tributylphenol polyethylene glycol- ether (30 moles of ethylene oxide) - 12 4 4, .2% cyclohexanone - 15 4 20 % mixture of xylenes 70 4 25 4 20 % From such concentrates, by diluting with water, they can be prepared emulsion every required concentration. b) Solutions a) b) c) d) active substance 80 and 10 4 5 % 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol ) molecular weight 400) - 70 4 - - N-methyl-2-pyrrolidone - 20 4 - - epoxidized coconut oil - - 1 % 5% gasoline) temperature range boiling point 160 to 190 °C) - - 94 % - These solutions are suitable for application in the form of very small drops. c) Granulate a) b) active substance 5 4 10 4 kaolin 94 4 - highly dispersed acids silica 1 4 - attapulgite - 90%

The active ingredient is dissolved in methylene chloride, the solution obtained is sprayed onto the carrier and the solvent is then removed in vacuo.

d) Dust a) b) active substance 2% 5% highly dispersed silicic acid 1% 5% talc 97% kaolin - 90%

By thoroughly mixing the carrier substances with the active substance, a powder for direct use is obtained.

Example F2

Examples illustrating the composition and preparation of formulations for solid active ingredients I (% = % by weight)

a) Wettable powder a) b) c) active substance 25% 50% 0.5% sodium lignin sulfone acids 5% 5 and 5% sodium lauryl sulfate 3% - -

sodium diiodobutylnaphthalenesulfo-

to - 6% 6% octylphenol polyethylene glycol ether (7 to 8 moles of ethylene oxide) 2 s 2% highly dispersed silicic acid 5% 27% 27% kaolin 67% - - sodium chloride - - 59.5% The active ingredient mixes well with ingredients and the mixture obtained s is ground in a suitable mill. A wettable powder is obtained, which can be mixed with water dilute to suspensions of any desired concentration. b) Emulsion concentrate a) b) active substance 10% 1% octylphenol polyethylene glycol ether (4 to 5 moles of ethylene oxide) 3 and 3% calcium salt of dodecylbenzenesulfonic acid 3% 3% castor oil polyglycol ether (36 mol ethylene oxide) 4% 4% cyclohexanone 30% 10% mixture of xylenes 50% 79% From this concentrate can be to prepare by diluting with water emulsion of any desired concentration c) Dust a) b) c) active substance 5% 8% 0.1% talc 95% - 99.9% kaolin - 92 i Dust for direct use is obtained by that the effective the substance is mixed with the carrier substances

and the mixture is then ground in a suitable mill.

d) Granulate prepared b) by extrusion a) active substance 10% ¹ » sodium lignisulfonate 2 » 2% carboxymethylcellulose 1% 1% kaolin 87% 96%. The active ingredient is mixed with the ingredients, the mixture is ground and moistened with water. This mixture is processed on an extruder and then the granulate is dried in a stream of air.

e) Coated granules active substance 3% polyethylene glycol (molecular weight 200) 3 8 kaolin 94%

The finely ground active ingredient is applied evenly to the kaolin, which is moistened with polyethylene glycol, in a mixer. In this way, a dust-free coated granulate is obtained.

y

f) Suspension concentrate a) b) active substance 40% 5% ethylene glycol 10% 10% nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6 i 1% sodium lignisulfonate 10% 5% carboxymethylcellulose 1% 1%

37% aqueous formaldehyde solution 0.2% 0.2% silicone oil in the form

75% aqueous emulsion 0.8% 0.8% water 32% 77%

The finely ground active ingredient is thoroughly mixed with the additives. This results in a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting with water.

Examples illustrating biological efficacy: For comparison, the results of biological examples B1 and B2 are always accompanied by the results of experiments with compound A.

CH,

I ³ o-ch-co-n(ch ₃ ) ₂ known with DE-OS 3

004 770, p. 12, no. 58.

Example Bl

Herbicidal effect in pre-emergence treatment

In the greenhouse, immediately after sowing the experimental plants in the trays intended for sowing, the soil surface is treated with a defective dispersion of active substances, obtained from 25% emulsion concentrate, or from 25% wettable powder in the case of active substances that cannot be processed into an erol.nf concentrate due to insufficient solubility. Two different concentrations of active substances were used, corresponding to 1 and 0.5 kg of active substance per 1 ha. The seed trays are kept in the greenhouse at a temperature of 22 to 25 °C and at 50 to 70% relative humidity and the experiment is evaluated for 3 weeks according to the following scale:

The tested compounds of formula I show excellent activity against monocotyledonous weeds of the grass type in this experiment, while crop plants such as wheat, barley, sugar beet, soybean and cotton remain undamaged or are only slightly damaged at the amount of active ingredient used. The comparison compound A is almost ineffective in this experiment.

up to 4 up to 7 up to 9 = plants do not germinate or are completely dead 3 = very strong effect 6 = medium effect 8 - slight effect = no effect

Results:

l

Compound number test plant 1.1 kg/ha 1.2 kg/ha 1.3 kg/ha 1.4 kg/ha 1 0.5 1 0.5 1 0.5 1 0.5 ryegrass (Lolium) 1 1 1 2 1 2 1 2 dogfish (Alopecurus) 1 1 1 1 1 2 2 2 sunflower (Digitaria) 1 1 1 1- 1 1 1 1 hedgehog (Echinochloa) 1 1 1 2 1 1 1 1 sorghum (sorghum) 1 1 1 1 1 1 1 2 Rottoboellia 1 1 1 1 1 1 1 1 soybean 9 9 7 7 9 9 9 9 cotton tree 9 9 9 9 9 9 9 9 sugar beet 9 9 9 9 9 9 9 9 Compound number 1.5 1 .6 kg/ha kg/ha experimental plant 1 0.5 1 0.5 lily (Lilium) dogwood 1 1 1 3 (Alopecurus) 1 2 2 4 dewdrop (Digitaria) hedgehogs 1 1 1 1 (Echinochloa) 1 1 1 3 sorghum (Sorghum) 1 1 1 2 Rottboellia 1 1 2 2 barley 7 9 7 8 wheat 6 8 8 9 Compound number 3.3 3 .4 3 .17 3 .18 A kg/ha kg/ha kg/ha kg/ha kg/ha experimental plant 1 0.5 1 0.5 1 0.5 1 0.5 ' 1 0.5 ryegrass (Lolium) 7 9 5 8 3 3 2 4 9 9 dogfish (Alopecurus) 4 4 3 4 1 2 1 2 8 9 sunflower (Digitaria) 2 4 1 1 1 1 1 1 4 6 hedgehog (Echinochloa) 2 2 2 6 1 1 1 1 9 9 sorghum (Sorghum) 1 3 2 7 1 3 1 2 9 9 Rottboellia 2 6 3 7 4 4 1 2 8 9 barley 9 9 8 9 8 9 8 9 9 9 wheat 8 9 7 9 4 4 3 5 9 9

Example B2

Herbicidal effect by post-emergence treatment (contact herbicide)

A number of weeds and cultivated plants, both monocotyledons and dicotyledons, are sprayed after emergence (at the 4 to 6 leaf stage) with an aqueous dispersion of the active substance at doses of 0.25, 0.5 and 1 kg of active substance per 1 ha by application to the plants and they are then maintained at a temperature of 24 to 26 ^U C and at 45 to 60% relative humidity. At least 15 days after treatment, the experiment is evaluated according to the same scale as given in the pre-emergence test.

In this test, the compounds of formula I also show excellent activity against monocotyledonous weeds of the grass type, while crop plants such as wheat, barley, sugar beet, cotton and soybean remain undamaged or are only damaged at higher application rates.

active substances. The comparison compound A remains almost ineffective in this experiment. Results: 1.3 kg/ha 1.4 kg/ha Compound number test plant 1.1 1.2 kg/ha kg/ha 1 0.*5 1 0.5 1 0.5 1 0.5 ryegrass (Lolium) 1 2 2 3 2 2 3 3 dogfish (Alopecurus) 1 2 2 3 1 2 2 6 · sundew (Digitaria) 1 1 1 1 1 1 1 1 hedgehog (Echinochloa) 1 1 1 1 1 1 1 1 sorghum (Sorghum) 1 1 1 1 1 1 1 2 Rottboellia 1 1 1 2 1 1 1 2 soybean 9 9 9 9 6 9 9 9 cotton tree 7 9 9 9 8 8 9 9 sugar beet 8 9 8 9 8 8 8 9 Compound number 1. 5 1.6 kg/ha kg/ha experimental plant 1 0.5 1 0.5 oats (Avenay 1 2 2 5 ryegrass (Lolium) 2 2 4 5 dogfish (Alopecurus) 1 2 4 8 sunflower (Digitaria) 1 1 1 2 Hedgehog (Echinochlosa) 1 1 1 1 sorghum (Sorghum) 1 1 1 3 Rottoboellia 1 1 1 3 barley 3 7 9 9 wheat 8 9 9 9

Compound number test plant 3.3 kg/ha 3.4 kg/ha 3.17 kg/ha 0.5 0.25 3.18 kg/ha A kg/ha 0.5 0.25 0.5 0.25 0.5 0.25 0.5 0.25 lily (Lilium) 1 2 3 3 1 1 1 2 7 9 dogfish (Alopecurus) 2 2 1 1 1 1 1 2 9 9 sunflower (Digitaria) 1 1 1 1 1 1 1 1 5 8 hedgehog (Echinochloa) 1 1 1 1 1 1 1 1 8 9 sorghum (Sorghum) 1 1 1 1 1 1 1 1 8 9 Rottoboellia 1 1 1 1 1 1 1 1 6 9

Continuation table Compound number 3.3 3.4 3.17 3.18 A kg/ha kg/ha kg/ha kg/ha kg/ha experimental plant 0.5 0.25 0.5 0.25 0.5 0.25 0.5 0.25 0.5 0.25

soybean 9 9 7 8 8 - 8 8 9 7 9 cotton tree 8 9 8 9 7 9 8 8 7 9 sugar beet 8 9 8 9 7 8 8 8 8 9

SUBJECT OF THE INVENTION

Claims (13)

Herbicidal composition, characterized in that, in addition to the carrier substances and / or other additives, it contains at least one 2-phenoxypropionic acid cyanamide of the formula I as active ingredient O — CH — CO — N — R CH, CN (I) in quench R is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkenyl or C 2 -C 4 alkoxyalkyl; and T represents a group of the formula or wherein X is fluoro, chloro, bromo or trifluoromethyl; Y is hydrogen, fluoro or chloro, and Z is nitrogen or a methine bridge 2. A composition according to claim 1, characterized in that it contains at least one compound of the formula I as active ingredient in which R is hydrogen or C1-C4alkyl and T is as defined in point 1. 3. A composition according to claim 2, wherein the active ingredient is at least one compound of formula I wherein R is C1 -C4 alkyl and T is as defined in point 1. 4. A composition according to claim 1 wherein T is as active ingredient at least a group of the formula X, Y and Z are as defined in 1, and R is as defined in 1. 5. A composition according to claim 1, wherein the active ingredient is at least one compound of formula I wherein T is 6-fluoroquinoxalin-2-yl or 6-chloroquinoxalin-2-yl, and R is as defined above. in point 1. 6. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula I wherein T is a group of formula and R is as defined in point 1. 7. A composition according to claim 4, wherein the active ingredient comprises at least one compound of formula (I) wherein T is a group of formula (4) wherein: X is chlorine, Y is fluorine and Z is nitrogen and R is as defined in 1. 8. A composition according to claim 1, wherein the active ingredient is at least one compound of formula I wherein R is C1-C4alkyl and T is 6-fluoroquinoxalin-2-yl. 9. A composition according to claim 1, wherein the active ingredient is at least one compound of formula I wherein R is C1-C4alkyl and T is 6-chloroquinoxalin-2-yl. 10. A composition according to claim 1, wherein the active ingredient is at least one compound of formula (I) wherein R is C1-C4alkyl and T is 6-chlorobenzoxazol-2-yl. 11. A composition according to claim 1, wherein the active ingredient is at least one compound of formula I wherein R is C1 -C4 alkyl and T is 5'-chloro-3-fluoropyridin-2-yl. group. 12. The composition of claim 1 wherein the active ingredient is at least one compound selected from the group consisting of 2-Q- (5-chloro-3-fluoropyridin-2-yloxy) N-cyano-N-methylamide. phenoxy] propionic acid, 2- [4- (5-Trifluoromethyl-pyridin-2-yloxy) -phenoxy] -propionic acid N-cyano-N-methylamide, 2- [4- (5-chloro-3-fluoropyridin-2-yloxy) phenoxy] propionic acid N-cyano-N-ethylamide, 2- [4- (6-chloro-quinoxalin-2-yloxy) -phenoxy] -propionic acid N-cyano-N-ethylamide, 2- [4- (6-Fluoro-quinoxalin-2-yloxy) -phenoxy] -propionic acid N-cyano-N-methylamide; 2- [4- (6-fluoro-quinoxalin-2-yloxy) -phenoxy] -propionic acid N-cyano-N-ethylamide 2- [4- (6-chloro-benzoxazol-2-yloxy) -phenoxy] -2- [4- (6-fluoroquinoxalin-2-yloxy) -phenoxy] -propionic acid and N-cyano-N-butylamide; propionic acids. 13. A process for the preparation of an active ingredient according to claim 1, wherein the 2-phenoxypropionic acid halide of the formula II is T-0 O-CH-CO-Hal (II) ch ₃ wherein T is as defined in formula I in point 1, Hal is chlorine or bromine, acting in the presence of an acid-binding agent with the cyanamide of formula III Η - N - R (III) t CN in which R is as defined in point 1.