CS207765B2 - Herbicide means and method of making the activa component - Google Patents

Abstract

1. Phenoxypropionic acid derivatives of the formula see diagramm : EP0003584,P20,F1 in which R represents hydroxyl, alkoxy which is optionally substituted by alkoxy, alkylthio, carbalkoxy, phenylmethylaminocarbonyl and/or halogen ; amino, hydrazino, alkylamino which is optionally substituted by alkoxy or dialkylamino, dialkylamino, alkenylamino, arylamino or N-aryl-N-alkylamino, it being possible for the aryl radical in each case to be substituted by alkyl, alkoxy, carbalkoxy, halogen and/or nitro, and furthermore represents a saturated heterocyclic ring with 5 or 6 ring members which is optionally substituted by alkyl and is bonded via nitrogen, or represents the radical of the formula see diagramm : EP0003584,P21,F2

Description

BACKGROUND OF THE INVENTION The present invention relates to a herbicidal composition comprising novel phenoxypropionic acid derivatives as an active ingredient. The invention further relates to a process for the preparation of these novel herbicidally active compounds.

It is already known that 3- (4-chlorophenoxy) -α-phenoxypropionic acid ethyl ester can be used to control weeds (cf. DOS 2,716,189). However, the efficacy of this substance is not always entirely sufficient, especially at lower doses.

The present invention relates to a herbicidal composition comprising, as an active ingredient, at least one novel phenoxypropionic acid derivative of the formula I,

Q ~ CH-C0 ~ R ~

C ⁰¹ arylcarbonyl "group or chlorine-substituted alkoxy having 1 to 4 carbon atoms, furthermore represents amino or alkoxy having 1-4 carbon atoms or dialkylamrnoskupinou having 1 to 4 carbon atoms in each alkyl radical substituted alkylamino having 1 to 4 carbon atoms, dialkylamino C 1 -C 4 alkyl, C 1 -C 4 alkenylamino or phenylamino or C 1 -C 4 -alkyl-N-alkylamino optionally substituted with C 1 -C 4 alkyl; carbon atoms, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl and / or chlorine.

The invention also provides a process for the preparation of phenoxypropionic acid derivatives of the formula I. The compounds of the formula I are obtained by reacting a phenoxypropionic acid chloride of the formula II in which:

R is hydroxy, optionally C 1 -C 2 alkoxy, C 1 -C 2 alkylthio, C 1 -C 2 alkoxycarbonyl, phenylmethylaminocarboxylic acid 207765

reacts with compounds of formula III,

HR (III) in which

R is as defined above, optionally in the presence of an acid binding agent and optionally in the presence of a diluent.

The process according to the invention will hereinafter be referred to as process a).

The compounds of formula (I) may also be prepared by other methods. Thus, a compound of formula I in which R is a hydroxyl group is obtained by providing a compound of formula Г

is reacted with bases in the presence of a diluent, then the reaction mixture is acidified (variant c) J.

Those compounds of formula I in which R is an alkoxy group with more than one carbon atom are obtained by:

Whose. O-CH-COOCH

reacted with alcohols of formula IV,

HOR ¹ (VI) in which:

R ¹ represents an alkyl group with more than one carbon atom, optionally in the presence of an alkoxide and optionally in the presence of a diluent (variant d).

Surprisingly, the phenoxypropionic acid derivatives according to the invention have very good herbicidal properties. Thus, the compounds according to the invention are distinguished by excellent activity against cyperus. They are also suitable for combating weeds in cereals, maize and rice. The substances according to the invention thus represent a valuable enrichment of the prior art.

The phenoxypropionic acid derivatives of the invention are generally defined by Formula I.

Examples of phenoxypropionic acid derivatives of the formula I according to the invention are:

3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -4-phenoxypropionic acid methyl ester, 3- (2,6-dichloro- 4-trifluoromethylphenoxy) -? - phenoxypropionic acid, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -? - phenoxypropionic acid isopropyl ester, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid n-butyl ester 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -? - phenoxypropionic acid, (2-methoxy-ethyl) -ethyl, 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -? Phenoxypropionic acid, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -ethyl- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid, (2-phenylmethylaminocarbonyl) ethyl ester, (2-Phenylmethylaminocarbonyl) ethyl ester 3- (2,6-dichloro-4-trifluoromethylphenoxy) - (-) - phenoxypropionic acid, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -, - (3-chloro-4-trifluoromethylphenoxy) -, - (phenoxypropionic) methylamide acid 3- (2,6-Dichloro-4-trifluoromethyl-phenoxy-α-phenoxy-propionic acid), (2-methoxy-4-trifluoromethyl-phenoxy) -4-phenoxy-propionic acid, 2-methoxy-ethylamide, dimethyl, dimethyl 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid, buten-2-ylamide 3- (2,6-dichloro-4-trifluoromethylphenoxy) -N-phenoxypropionic acid, (4-methylphenyl) amide 3 3- (2,6-Dichloro-4-trifluoromethyl-phenoxy) - N -phenoxy-propionic acid (4-methoxy-phenyl) -amide; - (4-ethoxycarbonyl-phenyl) - (2,6-dichloro-4-trifluoromethyl-phenoxy) - N -phenoxy-propionic acid; 3- (2,6-dichloro-4-trifluoromethylphenoxy) - N -phenoxypropionic acid amide, (4-chlorophenyl) 3- (2,6-dichloro-4-trifluoromethylphenoxy) - N -phenoxypropionic acid amide, (4- 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid, nitrophenyl) methylamide, 3- (2,6-dichloro-4-trifluoromethylphenyl) -, - phenoxypropionic acid piperide, pyrrolidide 3- [2 6-dichloro-4-trifluoromethylphenoxy-.alpha.-phenoxypropionic acid 3- (2,6-dichloro-4-trifluoromethylphenoxy) -4-phenoxypropionic acid piperazide, 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid pyrazolidide, 3- (2, 3-methylphenoxypropionic acid) pyrazolidide 6-dichloro-4-trifluoromethylphenoxy) -N-phenoxypropionic acid.

When 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid chloride and diethylamine are used as starting materials, the reaction sequence according to the invention (a) can be illustrated by the following reaction scheme:

If 3- (2,6-dichloro-4-trifluoromethylphenoxy) -? - phenoxypropionic acid methyl ester and sodium hydroxide are used as starting materials, the reaction sequence according to variant (c) can be illustrated as follows:

1) n & oh

2) HC 1

-N & Cl '

- CH _b OH

When 3- (2,6-dichloro-4-trifluoromethylphenoxy) -? - phenoxypropionic acid methyl ester and n-butanol are used as starting materials, the reaction sequence according to (d) is found to be as follows:

CI-CH-COOH

Br - CH - COOCH 3

AND

СНз (A)

The phenoxypropionic acid chloride required as starting material in carrying out process (a) according to the invention is precisely defined by formula II.

The compound is not yet known. However, it can be produced in a simple manner according to a method known in principle. Thus, the phenoxypropionic acid chloride of formula II is obtained by reacting the corresponding acid of formula I 'with a chlorinating agent such as thionyl chloride, optionally in the presence of a diluent such as ethylene chloride, at temperatures between 0 ° C and 50 ° C, preferably at temperatures between 10 ° C and 30 ° C.

The substituted phenoxypropionic acid of formula (I) is also not yet known. However, it can also be produced simply according to a method known in principle. Thus, the substituted phenoxypropionic acid of the formula I 'is obtained by reacting the corresponding methyl ester of the formula T

with strong bases, for example sodium hydroxide or potassium hydroxide, in the presence of a diluent such as methanol or water at temperatures between 20 ° C and 100% C, preferably at temperatures between 40 ° C and 80 ° C.

The substituted · phenoxypropionic acid methyl ester of formula Γ has also not been known. However, it can also be produced in a simple manner according to a method known in principle. Thus, the substituted phenoxypropionic acid methyl ester of the formula Γ is obtained by reacting the diphenyl ether of the formula IV

in the presence of an acid binding agent, such as sodium methoxide, sodium ethoxide, or potassium carbonate, in the presence of a polar diluent, such as methanol or acetonitrile, · at temperatures between. 20 ° C and 100 ° C, preferably 30 ° C and 80 ° C.

The diphenyl ether of formula IV has not yet been known. However, this compound can be produced in a simple manner according to a method known in principle. Thus, the diphenyl ether of formula IV is obtained by halogenating trifluoromethylbenzenes of formula VII,

in which

Hal is chlorine or bromine, in reaction with resorcinol of formula VIII

OH (Vin) in the presence of an acid binding agent as well as in the presence of a diluent at temperatures between 20 ° C and 200 ° C, preferably between 50 ° C and 150 ° C.

Suitable acid-binding agents are all customary bases. These preferably include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkaline earth metal hydroxides such as calcium hydroxide.

Suitable diluents are all customary inert aprotic polar solvents. These are preferably. amides such as phosphoric acid hexamethyltriamide, dimethylformamide or dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ketones such as methyl ethyl ketone; and nitriles such as acetonitrile and sulfolane.

Halogenated trifluoromethylbenzenes of formula VII are known.

The compounds useful below as starting materials in the process of the invention are treated with α-bromopropionic acid methyl ester of formula (V) as defined generally by formula (III). In this formula, R is preferably those already mentioned in the context of the description of the compounds of formula I according to the invention for R.

The compounds of formula III are known. Examples are:

water, methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-methyithioethanol, ethoxycarbonylmethanol, 2-ethoxycarbonylethanol, 2-phenylmethylaminocarbonylethanol, 2-chloroethanol, ammonia, hydrazine, methylamine ethylamine, n-propylamine, isopropylamine, 2-methoxyethylamine, 2-dimethylaminoethylamine, dimethylamine, diethylamine, di-n-propylamine, buten-2-ylamine, aniline, phenylmethylamine, 4-methylaniline, 4-methoxyaniline, 4- ethoxycarbonylaniline, 4-chloroaniline, 4-nitroaniline, piperidine, 2-methylpiperidine, pyrrolidine, piperazine, pyrazolidine, morpholine and 2-benzothiazolylmethylnine.

Suitable diluents for carrying out process a) according to the invention are all inert organic solvents. These preferably include ketones such as diethyl ketone and methyl isobutyl ketone, further nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran and dioxane, in addition aliphatic and aromatic hydrocarbons such as petroleum ether, benzene, toluene and xylene, and halogenated hydrocarbons such as methylene chloride carbon tetrachloride, chloroform and chlorobenzene; esters such as ethyl acetate; and formamides such as dimethylformamide.

In many cases where the compound of formula III is a liquid component, the addition of a diluent may be omitted. However, in these cases, the diluent may still be added.

All of the customary inorganic and organic acid acceptors used in the process according to the invention can be used as acid-binding agents. These preferably include alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, further lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines such as triethylamine, di-tertiary pyridine and diazabicyclooctane.

When the compound of formula III is an amine, an excess of the amine may serve as an acid binding agent.

The reaction temperatures can be varied within a wide range in process a) according to the invention. In general, temperatures between 20 ° C and 100 ° C, preferably between 30 ° C and 80 ° C, are employed.

In carrying out process a) according to the invention, preferably 1 to 2 mol or even a larger excess of the compound of the formula III and optionally 1 to 2 mol of the acid-binding agent are used per 1 mol of phenoxypropionic acid chloride of the formula II.

The isolation of the compounds according to the invention of the formula I is carried out by conventional methods. In general, the reaction mixture is mixed with the addition of an organic solvent, such as toluene or methylene chloride, after completion of the reaction, either directly or after prior concentration under reduced pressure, after which the organic phase is separated, washed and concentrated after drying. .

The methyl ester of phenoxybopionic acid which is required as starting material in carrying out process b) according to the invention is precisely defined by the formula Γ.

Phenoxypropionic acid methyl esters of the formula Γ have not yet been known. However, it can be produced simply in a manner known per se. This material is obtained, for example, by the method already described in detail in connection with the production of the starting materials for process a).

The reaction conditions to be followed in carrying out process c) according to the invention, as well as the bases and diluents used in the reaction, have already been described in detail in connection with the production of the starting materials for the process and according to the invention.

In carrying out process (c) according to the invention, preferably 1 to 2 mol of base is used per 1 mol of phenoxypropionic acid methyl ester of the formula (Γ). The isolation of the reaction product is carried out in the case of process (c) according to the invention by conventional methods. In general, after completion of the reaction, the reaction mixture is poured into water, the solution is filtered, the filtrate is then acidified and the acid which precipitates in solid form is filtered off.

In the process (dj) according to the invention, the starting material is the phenoxypropionic acid methyl ester which has already been mentioned in connection with process (c) according to the invention.

In process (d) according to the invention, the alcohols used as starting materials are further used. are generally defined by formula VI. In formula VI, R1 is preferably a straight or branched alkyl radical having 2 to 4 carbon atoms.

Examples of compounds of Formula VI are: ethanol, n-propanol, isopropanol, isobutanol, n-butanol, sec-butanol and tert-butanol.

Alcohols of the formula VI are known substances.

In process (d) according to the invention, the reactants of the formula VI used in excess can simultaneously serve as diluents. However, it is also possible to use inert organic solvents as diluents.

The reaction according to process (d) according to the invention is preferably carried out in the presence of an alkoxide such as sodium methoxide.

The reaction temperatures can be varied within a wide range in process (d) according to the invention. In general, temperatures between 20 ° C and 200 ° C, preferably between 60 ° C and 120 ° C, are employed.

In carrying out process (d) according to the invention, an excess of the alcohol of the formula VI is used per mole of the phenoxypropionic acid methyl ester of the formula Г as well as a catalytic amount of the alkoxide. The reaction products are isolated by conventional methods.

In general, the reaction mixture is concentrated after completion of the reaction, the residue is stirred with an organic solvent, the solution is filtered, the filtrate is washed and, after drying, concentrated.

The active compounds according to the invention influence the growth of plants and can therefore be used as defoliation agents, desiccants, weed control agents, germination inhibition agents and in particular as weed control agents.

In the broadest sense, weeds are understood to mean all plants that grow where they are undesirable. Whether the active compounds according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants:

dicotyledonous weeds of genera:

mustard (Sinapis), cress Lepidium), Bedstraw (Galium), Chickweed (Stellaria), Chamomile (Matricaria), Stem (Anthemia), Stink (Galinsoga), Goosefoot (Chenopodium), Nettle (Urtica), Ragwort (Senecio), Pigweed (Amaranthus), purslane (Portulaca), beetroot (Xanthium), bindweed (Covolvulus), broom (Ipomoea), moss (Polygonum), gathering (Sesbania), ambrosia (Ambrosia), thistle (Cirsium), thistle (Carduus), milk (Sonchus), Eggplant (Solanum), Mustard (Rorippa), Rotala, Lindernia, Deadnet (Lamium), Speedwell (Veronica), Abutilon (Abutilon), Emex, Durman (Datura), Violet (Viola), Hemp (Galeopsis), poppy (Papaver), cornflower (Centaurea).

dicotyledonous plants of genera:

cotton (Gossypium), soybean (Glycine), beet (Beta), carrot Daucus), bean (Phaseolus), peas (Pisum), potatoes (Solanum), flax (Linum), bitterwort (Ipomoea), vetch (Vicia), tobacco (Nicotiana), tomato (Lycopersicon), peanut (Arachis), kale (Brassica), lettuce (Lactuca), cucumber (Cucumis), gourd (Cucurbita);

monocotyledonous weeds of genera:

hedgehog (Echinochloa), shear (Setaria), millet (Panicům), tree frog (Digitaria), timothy (Phleum), meadow-grass (Poa), fescue (Festuca), eleusine (Eeleusine), Brachiaria, rye (Lolium, brome) (Bromus) , oat (Avena), flathead (Cyperus), sorghum (Sorghum), wheatgrass (Agropyron), hawkfish (Cynodon), Monocharia, Fimbristylis, arrowhead (Sagittaria), Eleocharia, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyinecenis ), foxtail (Alopecurus), chundelka (Apera);

Monocotyledonous plants of genera:

rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugarcane (Sacharum), pineapple (Ananas) , asparagus (Asparagus), garlic (Allium).

However, the use of the active compounds according to the invention is by no means restricted to these genera but also to other plants in the same way.

The compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial and railway surfaces and on roads and squares, possibly with trees. The compounds of the invention may also be used to control weeds in long-term crops such as forest and ornamental trees, fruit trees, vineyards, citrus, butternut, banana, coffee, tea, rubber, coconut, cocoa, and other crops. berry plants and on hop gardens, selective weed control in annual crops.

The active compounds according to the invention are particularly suitable for combating weed (Cyperus), in addition they can be used very well for combating weeds in cereals, maize and rice.

The active compounds according to the invention can be used as such or in the form of compositions also in admixture with known herbicides for controlling weeds, with the use of ready-to-use compositions or tankmix mixtures.

The active compounds can be used in the form of customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension or emulsion concentrates, active substances impregnated with natural and synthetic substances and fine particles coated with polymeric substances .

Said compositions are prepared in a known manner, for example by mixing the active compounds with fillers, i.e. liquid solvents and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents.

If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalene, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are: natural stone meal, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomite, and synthetic stone meal, such as highly dispersed silicic acid, alumina and silicates; crushed and fractionated natural stone materials, such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic material, such as sawdust, coconut shells, are suitable carriers for the preparation of granulates. , corn sticks and tobacco stalks.

Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, for example alkylaryl polyglycol ether, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates, and as dispersants, methylcellulose and lignin, sulfite.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 05% by weight, preferably between 0.5 and 90% by weight of active ingredient.

The active compounds according to the invention can be used in the compositions together with other known active compounds, such as fungicides, insecticides and acaricides.

The active compounds may be administered as such, in the form of their compositions or in dosage forms prepared by further dilution thereof, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. Application is carried out in the usual manner, for example by spraying, dusting, sprinkling and watering.

The active compounds according to the invention can be applied both after the emergence of the plants and before the emergence of the plants. Pre-emergence results in better selectivity than post-emergence.

The application rate of the active ingredient can vary within wide limits. This amount depends essentially on the type of effect desired. In general, the application rate is between 0.1 and 25 kg of active ingredient per ha, preferably between 0.25 and 10 kg / ha.

The compounds according to the invention have not only herbicidal properties but also have fungicidal activity.

The good herbicidal activity of the active compounds according to the invention results from the following examples.

Example A

Pre-emergence test:

solvent:

parts by weight of acetone emulsifier:

part by weight of alkylaryl polyglycol ether

The active ingredient is prepared by mixing one part by weight of the active ingredient with the indicated amount of solvent, adding the indicated amount of emulsifier and diluting the concentrate to the desired concentration with water.

The seeds of the test plants are sown in normal soil and after 24 hours are poured with the active ingredient. The amount of water per unit area is expediently constant. The concentration of the active ingredient in the formulation is not important, only the consumption of active ingredient per unit area is critical. After three weeks, the degree of damage to the test plants is determined and expressed as a percentage of the development of the untreated control plants. It means:

% - no effect (as in untreated control plants),

100% - total destruction of plants.

The active substances, the application rates and the results are given in Table A.

Pre-emergence test effective used Siná- Matri- Galin- Stella- Cheno- Cype- dog- fun- funnel amount of pis caria soga ria podium russia nikicum kg / ha

OOOOOOOCDOO 00 οοαοοοοοοοο СО СО

0000000000

OOOOOOOOOO

WHAT

οοοοοοαοοο

ОООоОООСОСЛОООСО ΗΗ Y-l оооооооооо OOCCQCD ^ (COCJOO) гН тН т * Ч гН

оооооосооо

О? СЛ О со 50 СО се О 00

Ю LD in 1Ω Ю 1П Ю 1П ΙΩ LO '(O> o

СЛ> ω

*

Example В

Post-emergence test: solvent:

parts by weight of acetone emulsifier:

part by weight of alkylaryl polyglycol ether

The active ingredient is prepared by mixing 1 part by weight of the active ingredient with the indicated amount of solvent, adding the indicated amount of emulsifier and diluting the concentrate with water to the desired concentration.

The prepared active ingredient is sprayed on 5-15 cm high test plants to achieve the consumption of active ingredient per unit area shown in the table below. The concentration of active ingredient in the spray is selected to consume 2000 liters of water containing the amount of active ingredient listed in the table per hectare. After three weeks, the degree of damage to the plants is evaluated and expressed as a percentage of the development of the untreated control plants. 0% means no effect (as in untreated control plants), 100% means total destruction of the plants.

The active substances, consumption and results are shown in Table B.

· 2 ·

I ω а ω

СЛ Д ч

no \ гН д СО д ч д О ьо F ч Д -ч Ф го д н ч ω В д Й ω

Си

AND

Д] ω cd ω ч

I д

д cd ьо о сл

4d Д Д> ω 'Д Honors

4ti -ч 'СО

Example C

Defoliation and drying of leaves in cotton / growth suppression solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient composition, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Cotton plants are grown in a greenhouse until the fifth leaf is fully developed. At this stage, the plants are sprayed with the active ingredient compositions until wetted. After one week, the degree of fallen leaves and dried leaves is evaluated in comparison with control plants. It means:

no sheets drying, no leaves fall,

4- weak sheet drying, slight fall of sheets, + + strong sheet drying, strong sheet fall, 4-4-4- very strong sheet drying, very strong sheet fall.

After 3 weeks, the plant growth is measured and the plant growth suppression is calculated as a percentage of the control plant growth. 100% means no growth state (rest state) and 0% means growth state corresponding to growth of control plants. Growth suppression is a measure of plant re-ejection after defoliation or leaf drying. In practice, suppression of plant re-expulsion is highly desirable.

The test results are shown in Table C below.

Table C active substance defoliation concentration or growth inhibition% leaf drying%

(1) 0.05 4-4-4- 100 ALIGN! (2) 0.05 4- —H + 85 Italy (23) 0.05 + 85 (7) 0.05 4-4- 85 Italy (9) 0.05 4—1 — l · __ *) 0,025 + 4- _ *) 0.0125 + - ^ *) (10) 0.05 + 35 (8) 0.05 4-4 · 60 Italy (20) 0.05 4 -! - h 100 ALIGN! Italy (11) 0.05 + 70 (4) 0.05 4-4- 65 (12) 0.05 4- 4- 85 Italy (27) 0.05 4—1 — l- 100 ALIGN!

none available - numbering of active substances values correspond to numbering in the examples illustrating the method of production of active substances

List of active substances:

(1)

(3)

Cl

Examples illustrating a process for the preparation of active substances

Example 1

To a solution of 97 g (0.3 mol) of 2,6-dichloro-4-trifluoromethyl-3'-hydroxydiphenyl ether and 17.8 g of sodium methoxide in 400 ml of methanol is added dropwise at 45 to 50 ° C over 2 hours The mixture was allowed to stir for 3 hours at 45-50 ° C and then worked up by concentrating the reaction mixture, taking up the residue with 1 liter of methylene chloride, filtering the solution, then successively with a dilute aqueous solution. Sodium hydroxide and water and dried and concentrated to give 59.0 g (64.4% of theory) of 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -α-phenoxy-propionic acid methyl ester as a brownish oil. 20 = 1.5206).

Analysis for C17H13Cl2F30d calculated:

C 49.9 o / o, H 3.2 θ / ο, Cl 17.4%, found:

C 49.6%, H 3.6%, Cl 16.8%.

2,6-Dichloro-4-difluoromethyl-3‘-hydroxydiphenyl ether required as starting material and corresponding to the formula

is produced as follows:

To a mixture of 330 g (3 mol) of resorcin and 111 g (1.5 mol) of calcium hydroxide in 2 liters of dimethylsulphoxide, 358 g (1.5 mol) of 3,4,5- -g-chlorobenzolrichloride. The reaction mixture was then stirred at 130 ° C for a further 8 hours. After cooling to room temperature, the reaction mixture was poured into 7 L of water, whereupon the reaction product precipitated as an oil. This oil is extracted with 3 liters of toluene, the organic phase is separated off and, after drying, concentrated. The residue is distilled. 350 g (73% of theory) of 2,6-dichloro-4-difluoromethyl-3'-hydroxydiphenyl ether are obtained in the form of a solid, m.p. 64-65 ° C.

Boiling point 123-130 ° C / 20 Pa

Analysis:

Calcd for C13H7Cl2F3O2:

C 48.3%, H 2.2%, Cl 22.0%, found:

C 48.3%, H 2.3%, Cl 21.8%.

Example 2

A mixture of 20.5 g (0.05 mol) of methyl 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -α-phenoxypropionic acid, 0.1 g of sodium methoxide and 150 ml of isobutanol was refluxed for 9 hours. . Thereafter, the excess isobutanol is distilled off at atmospheric pressure. The reaction mixture is then worked up by concentration, the residue is stirred in 500 ml of methylene chloride, then the methylene chloride solution is washed twice with water and, after drying, concentrated. In this way, 17.5 g (77.6% of theory) of 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -α-phenoxy-propionic acid isobutyl ester are obtained in the form of a yellowish oil.

Analysis:

Calcd for C20H19Cl2F5O4:

C 53.2%, H 4.2%, Cl 15.7%, found:

C 53.1%, H 4.5%, Cl 15.4%.

Example 3

To 27.5 g (0.067 mol) of 3- (2,6-dichloro-4-trifluoromethylphenoxy-n-phenoxypropionic acid methyl ester) and 70 ml of methanol were added 30 ml of water and 10 ml of concentrated sodium hydroxide solution and the mixture was allowed to stir. 5 hours at 50-60 [deg.] C. The reaction mixture is then worked up by pouring it into 1 liter of water, filtering the solution, acidifying the filtrate and filtering off the precipitated crystalline product to give 21.7 g (82%). 0% of theory) 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid as an ivory solid with a melting point of 151 ° C.

Example 4

To a solution of 11.3 g (0.05 mol) of (2-aminoethyl) methyl ether in 10 ml of pyridine was added dropwise a solution of 27.7 g of 3- (2,6-dichloro-4-trifluoromethylphenoxy) at 0-5 ° C. The α-phenoxypropionic acid in 30 ml of toluene is stirred overnight at room temperature and then treated by adding 350 ml of toluene, followed by washing the toluene solution successively with dilute aqueous sodium hydroxide solution and water until It is dried and concentrated to give 19.7 g (87.2% of theory) of (2-methoxy-ethyl-3- (2,6-dimethyl-4-trifluoro-4-trifluoride) fluoromethylphenoxy) -? - phenoxypropionic acid as a colorless solid, m.p. 90-100 ° C.

The starting material required for 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid chloride of the formula is prepared as follows:

To a solution of 98.2 g (0.249 mol) of 3- (2,6-dichloro-4-trifluoromethylphenoxy) -α-phenoxypropionic acid and 3 ml of dimethylformamide in 200 ml of ethylene chloride is added dropwise 35.5 g (0.298 mol) at room temperature. thionyl chloride. The reaction mixture was then slowly heated to reflux and further refluxed for 4 hours. The reaction mixture is then worked up by filtration and the filtrate is concentrated. 88.5 g of 3- (2,6-dichloro-4-difluoromethylphenoxy) -α-phenoxypropionic acid chloride are thus obtained in the form of an orange-colored oil.

Analysis:

calculated:

C 46.4%, H 2, -4%, Cl 25.8%,

Cl found:

C 45.7%, H 3.0%, Cl 2 → 0%.

In accordance with one or more of the processes described above, the substances listed in Table 1 are prepared.

207785 melting point [° C] or refractive index [n _D o]

Table 1

example no.

¹⁰

CH2 - О — C2H5 /

—O — CH \

CH2-O-C2H5

-O-CH-CO- / V г. ]

CH2-NH-CH2-CH-CH2

Cl

136

1,5476

1,5585

1.5342

1,5062

67—68

120

100 ALIGN!

149

63—64

116

207785 Example R

C.

melting point [° C] or refractive index [n _D ²⁰ ]

-NH-O 2 H 4 -N (C 6 H 5 J 2 O);

CH2-Cl of -O-CH

CH2-Cl

161

188

39-40 —NH2 - N (CH3) 2

114—115

89—90

23 24 ··? <} CH _b 25 -p 26 27 Mar: —NH — NH2 —О — СНг — COOO2H5

105—106

82—84

1,5393

1,5167

Claims (2)

OBJECT OF THE INVENTION A herbicidal composition, characterized in that it contains at least one phenoxypropionic acid derivative of the formula I as an active ingredient, Cl 0 < H &gt; R is hydroxy, optionally C 1 -C 2 alkoxy, C 1 -C 2 alkylthio, C 1 -C 2 alkoxycarbonyl, C 1 -C 4 phenylmethylaminocarbonyl or chloro-substituted alkoxy, furthermore amino or C 1 -C 4 alkoxy; (C 1 -C 4) alkoxy or (C 4 -C 4) dialkylamino substituted by C 1 -C 4 alkylamino, (C 1 -C 4) dialkylamino, (C 4 -C 4) alkenylamino or phenylamino optionally N -phenyl-N-C 1 -C 4 alkylamino, wherein the phenyl radical may be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, and / or or chlorine. 2. A process for the preparation of an active ingredient according to claim 1, characterized in that the phenoxypropionic acid chloride of the formula II Q-CH-COCt AND CH ₅ (u) reports in the reaction of formula III, HR with compounds of the general formula in which R is as defined above, optionally in the presence of a selinium-binding agent (III) and optionally in the presence of a diluent.