CS198263B2 - Herbicide - Google Patents

Description

The invention relates to herbicidally active compounds, to compositions containing them, and to a process for the preparation of these compounds.

It has been found that the compounds of formula (I)

Cl

O — CH-R

I ch ₃ (1), in which

R is -CH ₂ 0H, -COOH, -COOKat, -C00R ,, -C0NH ₂ -CONHOCHj or -CONHCH ₂ CK ₂ OH, where

R 1 represents an alkyl group having 1 to 5 carbon atoms optionally interrupted by an oxygen atom and

Cat is equivalent to an inorganic or organic cation, having herbicidal properties.

Kat is in particular an alkali metal cation (e.g. sodium or potassium cation), an equivalent of an alkaline earth metal cation or an ammonium cation, e.g. a cation derived from ammonia or ammonia substituted by one or more methyl, ethyl, propyl, isopropyl or hydroxyethyl groups.

Typical compounds of the invention include:

156-158 ° C, 2- [4- / 4-chlorophenoxymethyl / phenoxy] propionic acid, 2- [4- / 4-chlorophenoxymethyl / phenoxy] propionic acid, methyl ester, m.p. 4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid, m.p. 47 ° C, 2- [4- / 4-Chloro-phenoxymethyl / -phenoxy] -propionic acid isopropyl ester, M.p. (phenoxy) propionic acid, melting point 66 ° C, 2 'L4- (4-chlorophenoxymethyl) phenoxy] propionic acid isobutyl ester, m.p. melting point 40 ° C,

2-Methoxyethyl 2- [4- (4-chlorophenoxymethyl) phenoxy] propionic acid, m.p. 58 DEG C., oily 2- (2-methoxyethoxy) ethyl 2- [4- (4-chlorophenoxymethyl) phenoxy] Jp petroleum acids.

2- [4- (4-chlorophenoxymethyl) phenoxy] propionaraid, m.p. 143 [deg.] C,

N '2-hydroxyethyl "2- [4- / 4" chlorophenoxymethyl / -phenoxy] -propionamide m.p. 110 ⁰ C, of 2 - / 4 * / 4-chloro- phenoxymethyl / fenoxyjpropionové acid such as sodium salt, mp 250 M.p. 222 ° C; ammonium salt m.p. 160-165 ° C; diraethylammonium salt m.p. 128-136 ° C; diethylammonium salt mp 133 ° C; cyclohexylammonium salt m.p. 187 DEG C., morpholinium salt, melting point 123 DEG-124 DEG C., imidazolium salt, melting point 124 DEG C., and

2-hydroxy-1-propyl-dimethylanionium salt, m.p. 168 ° C;

2- [4- (4-chlorophenoxymethyl) phenoxy] propanol, m.p.

Some of the compounds of formula I are known from DOS. These known compounds, as well as the compounds of formula (I) which have not been described so far, can be prepared according to the procedure cited above by DOS or other methods known per se.

The following procedures are expediently used to prepare said substances

^From II / in which

R is as defined above and

X represents a residue cleavable as an anion, preferably chlorine or bromine, and is reacted with 4-chlorophenol of formula IIIa

Cl

OH and an acid binding agent, or the corresponding phenoxide, and the obtained compound of formula IV, ^{C, _ <@ HOCH} 2 / O / ^{CH HO_ "R}

CH ₃

If Z is Z, the radical R is optionally converted in a manner known per se into another radical R.

The reaction of the compound of formula IX with the compound of formula III is preferably carried out in an inert solvent, for example an alcohol. The reaction temperature is preferably between 0 ° C and the boiling point of the reaction mixture.

When R is an ester or carbamoyl group, the resulting compounds can be saponified, preferably with a base, to give the corresponding acid or salt of the corresponding base.

Reaction of the corresponding ester with the corresponding amines leads to the amides of the invention. The alcoholate catalysed reaction yields other esters of the invention from the primary esters formed,

Hydrolysis of esters or amides, preferably by treatment with alkaline reagents, results in R-containing acids having a carboxyl group or a -COO-cation. Salts of these acids can be converted to the desired esters by treatment with customary alkylating agents, for example dialkyl sulfates.

It is also possible to prepare from the acids by reaction with 1,1-carbonyldiimidazole the iraidazolides, and from them, by reaction with alcohols or amines, the corresponding esters or amides. Esters can be further prepared by reacting acids with alcohols in the presence of carbodiimides.

The corresponding compounds of formula (IV) in which R is an esterified carboxyl group, which is reduced to a hydroxymethyl group by treatment with complex hydrides, preferably lithium aluminum hydride, can also be used to prepare those compounds in which R is CH 2 OH.

The following section describes another method of preparing the above compounds:

Phenol of formula V

Cl ^ O) ^{'OCH2 <@ HO} H / V / is in the form of a phenolate or in the presence of an acid binding agent is reacted with a propionic acid derivative, of formula VI

X-CH-R

I / VI /.

CH ₃ to give compounds of the formula IV, which is then optionally further processed as described above in process 1 /.

This reaction is preferably carried out in an inert solvent, wherein the λ temperature is between 0 ° C and the boiling point of the reaction mixture.

The starting materials of formula (II) above may be prepared from the corresponding alcohols of formula (VII) and ( ₃₎

O-CH-R

/ VII / »CH ₂ OH replacing the hydroxyl group in the hydroxymethyl group, for the rest of X, caused utilizing conventional crane.

Surprisingly, compounds of formula II in which X is bromine can be prepared from compounds of formula VIII

98263

O-CH-R (VIII)

CH ₃ bromination with bromine under illumination or with bromine in the presence of a catalyst (for example azoisobutyric acid nitrile). Despite all expectations, both the propionic acid group and the benzene ring in the starting material molecule are brominated only to a negligible extent. Said reaction is carried out in an inert solvent, preferably a low polar solvent, such as carbon tetrachloride, chloroform, benzene or cyclohexane, preferably at the boiling point of the reaction mixture.

Surprisingly, the compounds of the formula II in which X represents a chlorine or bromine atom can also be obtained by halomethylation of the compounds of the formula IX ch ₃

O-CH-R (IX), and so on. these compounds are reacted with conventional halomethylating agents, preferably a combination of formaldehyde and hydrogen chloride or dichlorodimethyl ether, in an inert solvent such as cyclohexane or benzene at a temperature of about 0 to 80 ° C, preferably at room temperature.

The phenols of formula (V) can be prepared in a manner known per se by lowering the lower alkyl ester of phenol-carbonic acid with methyl chloromethyl ether, reacting the reaction product with 4-chlorophenol of formula (III) and liberating the phenol of formula (V) from the carbonate.

According to the above-mentioned DOSs, the compounds described in these publications possess valuable pharmacological properties, for example, a cholesterol-lowering effect.

As has now been found, the compounds of the formula I are surprisingly also characterized by a strong herbicidal activity, in particular against weed grass, for example against alopecurus myosuroides, deaf oats (Avena fatua), rye (Lolium) and wild millet species. The selectivity of these substances is so pronounced that even when applied in higher amounts, the dicotyledonous crop plants are only very slightly damaged in the worst case. The active compounds according to the invention can control grass weeds even in some monocotyledon crops such as maize, rice, barley, oat and wheat.

The novel compositions of the invention are suitable for both preemergence and postemergence applications, with consumption ranging from 0.1 to 3 kg, preferably from 0.3 to 1.5 kg / hs.

For application purposes, the compounds of formula (I) are formulated in conventional manner using conventional excipients and / or carriers into appropriate formulations, for example, concentrates, such as emulsion concentrates or suspendable powders, in which case the active compound content is approximately 10 and 95% by weight, or for dusting, emulsions, granulates and solutions which can be applied immediately and which contain between about 0.01 and 20% by weight of active ingredient.

The concentrates are diluted with water to the desired application concentration of about 0.01 to 3% by weight.

The following are examples of compositions according to the invention.

1. Suspensible powder

X of 2- (4- (4-chlorophenoxymethyl) phenoxy) propionic acid by weight

X by weight of kaolin

X by weight of colloidal silicic acid

% By weight of calcium lignin sulphonate dispersant

X by weight of sodium tetrapropylenebenzenesulfonate as wetting agent

The above ingredients are ground and the composition obtained is suspended in water to give a concentration of active ingredient of 0.01 to 3%.

2. Dust

X by weight sodium 2- [4- (4-chlorophenoxymethyl) phenoxy] propionate

7, by weight of talc 1 From methylcellulose by weight

The dusts are prepared by grinding the above ingredients to homogeneity.

3. Emulsion. % w / w ethyl acetate / methoxyethyl or 2- [4- (4-chloro-enoxymethyl) -phenoxypropionic acid methyl ester concentrate

7 _{and by} weight of liquid solvent mixture of high boiling aromatic hydrocarbons (Shell ”sol A)

6.5% Tensiofix AS emulsifier

3.5 From a Tensiofix DS weight emulsifier

An emulsion concentrate is prepared from the above ingredients in a conventional manner.

The following tests demonstrate the efficacy of the compositions according to the invention:

Test A

The above-mentioned suspensible powder containing 2- [4- (4-chlorophenoxymethyl) phenoxy] propionic acid as active ingredient is applied pre-allergen at a rate of 0.3 kg / ha in maize against Echinochloa crus-galli maize.

In the above described application, a 90Z effect is obtained.

When applied at the same dose of sodium, respectively. the diethylammonium salt of the above acid is obtained in the above-described test 882, respectively. 862 effect.

T e s t B

Emulsion concentrates containing the following compounds according to the invention as active ingredients are prepared as described above:

2 - [[4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid ethyl ester

B 2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid methoxyethyl ester

C 2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionhydroxamic acid methyl ester

D 2-L '- (4-chlorophenoxymethyl) phenoxy] propionic acid 2-hydroxyethylamide

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid n-amyl ester

F 2- [4- (4-chlorophenoxymethyl) phenoxy] propan-1-ol

G 2-L4- (4-chlorophenoxymethyl) -phenoxy] propionic acid methyl ester

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid amide.

The prepared preparations are applied in the form of spray suspensions post-allergenic at doses corresponding to 0.5 kg of active ingredient per hectare against Alopecurus, Avena fatua and Echinochloa crus-galli in barley culture.

The herbicidal effect attained, expressed as a percentage of the condition in the untreated control, is as follows:

Table of active substance

A β

C

E

F

G

H

Herbicidal effect / 2 /

The crop plants show no signs of damage in this treatment.

For some application purposes, it may be advantageous to add other herbicides to the compounds of the invention. Examples of such herbicides that may be added to achieve advantageous properties and effects are:

2.3.6- triehlorobenzoic acid and its salts,

2.3.5.6- tetrachlorobenzoic acid and its salts,

2-N-ethoxy-3,5,6-triethylbenzoic acid and its salts,

2-methoxy-3,6-dichlorobenzoic acid and its salts,

2-methyl-3,6-dichlorobenzoic acid and its salts,

2.3-Dichloro-6-methylbenzoic acid and its salts

2.4- dihlorophenoxyacetic acid and its salts and esters,

2,4,5-trichlorophenoxyacetic acid and its salts and esters, 2-methyl-4-chlorophenoxyacetic acid and its salts and esters,

2- (2,4,3-trichloro-phenoxyzpropionic acid and its salts and esters, 2- (2,4-dichlorophenoxy) butyric acid and its salts and esters,

4- (2-methyl-4-chlorophenoxy) butyric acid and its salts and esters,

2,3,6-trichlorophenylacetic acid and its salts,

36-endoxohexahydrophthalic acid, dimethyl '2,3,5,6-tetrachloro-terephthalate, trichloroacetic acid and its salts,

2.2- di-chloropropionic acid and its salts,

2,3-di-chlorobutyric acid and its salts, ethyl-NN-di-n-propyl / thiolcarbamate, propyl, N'-di / n-propyl-thiolcarbamate, ethyl-N-ethyl-N- / n-butyl / thiolcarbamate, propyl N-ethyl-N- (n-butyl) thiolcarbamate,

2-chlorallyl-N, Ν-diethyldithiocarbamate, salts of N-methyldithiocarbamic acid,

5-ethylhexahydro-1H-azepine-1-carbothioate,

S-4-chlorobenzyl-N, N-diethylthiocarbamate, isopropyl-N-phenylcarbamate, isopropychlorophenyl / carbamate,

4-chloro-2-butyl-1-N- (m-chloro-phenyl) -carbamate, methyl-M- (3,4-dichlorophenyl) carbamate, methylisanilicarbamate>

dinitro-o- (sec-butyl) phenol and its salts, pentachiorophenol and its salts,

3- (4-isopropylphenyl) -1,1-dimethylurea,

3- / 3,4-dichlorophenyl-1,1-dimethylurea,

3-phenyl-1,1-dimethylurea,

3- (3,4-Dichlorophenyl) -3-methoxy-1,1'-dimethylurea,

3- (4-chlorophexyl) -3-hethoxy-1,1-dimethylurea,

3- (3,4-Dichlorophenyl) -1-n-butyl-1-methylurea,

3- (3,4 * -dichlorophenyl) -1-methoxy-1-methylurea,

3- (4-Chlorophenyl) -1-methoxy-1-methylurea

3- (3,4-Dichlorophenyl) -1,1,3-trimethylurea,

3- (3,4-dichlorophenyl) -1,1-diethylurea,

1- (2-methylcyclohexyl) -3-phenyl urea,

1- (5-tert-butyl-1,3,4'-thiadiazol-2-yl) -3,3-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea,

3- (3-Chloro- N -methoxyphenyl) -1,1-dimethylurea, dichloromethane,

2- ch1or -4 _and 6-bis / ety1amino / -s-tri amine is present

2-chloro-A-ethylamin-4-isopropylamino-s-triazine,

2-chloro-4,6-bis (methoxypyramino) -s-triazine,

2-methoxy-4,6-bis (isopropylamino) -s-triazine,

2-methylmercapto-4,6-bio (isopropylamino) -α-triazine,

2-methylmercapto-4,6-bis-ethyl-arylamino / -s-triazine,

2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine,

2-chloro-4,6-bis (isopropylamino) -s-triazine,

2-methoxy-4,6-bis (ethylamino) -s-triazine,

2-Methoxy-4-ethylamino-6-isopropylamino-s-triazine

2-methylmercapto-4- (2-methoxyethylamino) -6-isopropylaraino-s-triazine,

2- [4-chloro-6-ethylamino-s-triazin-2-yl] amino-2-methylpropionyltrile,

4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5 (4H) -one,

3-cyclohexyl-6-dimethylamino-1-methyl-s-triazine-2,4- (111,3H) -dione,

3-methyl-4-amino-6-phenyl-1,2,4-triazin-5 (4H) -one,

244-dichloro-4'-trodiphenyl ether,

2,4,6-trichloro-4'-ni trodiphenylether _r

2,4-dichloro-6-fluoro-4'-nitro-phenylether,

3-methyl-4-nitrophenyl ether,

3.5- dime ty1-4 * -nitrodiphenyleter, *

2,4-dinitro-4-trifluoromethyl diphenyl ether,

2,4-Dichloro-3'-methoxy-4 ^- nitrophenyl ether,

2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether,

2-chloro-4-trifluoromethyl-3'-ethoxy-4'-nitro-phenylether,

2-Chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitro-phenyl ether

2-chloro-4-trifluoromethyl-3- (1-ethoxycarbonyl) ethoxy-4'-trodiphenyl ether,

N- (3,4-Dichloro-phenyl) -propionate d,

N- (3,4-dichlorophenyl) methacrylamide,

N- (3-chloro-4-methylphenyl) -2-methylpentanamide,

N- (3,4-Dichlorophenyl) trimethylacetamide amide,

N- (3,4-dichlorophenyl) -N-dimethyl-amide,

N-isopropyl-N-phenylene with d,

N-n-butoxymethyl-N- (2,6-diethylphenyl) chloroacetamide,

N-n-methoxyethoxy-N- (2,6-diethylphenyl) chloroacetamide,

5-bromo-3-sec-butyl-6-methyluracil,

5-bromo-3-cyclohexyl-1,6-dimethyluracyl,

3-cyclohexyl-5,6-trimethylenuracil,

5-bromo-3-isopropyl, -6-methyluracil »

3-tert-Butyl-5-chloro-6-methyluracyl,

2,6-dichlorobenzonitrile, diphenylacetonitrile,

3,5-dibromo-4-hydroxybenzonitrile,

3,5-diiodo-4-hydroxybenzone.itri 1,

2-chloro-N, N-diallylacetamide,

N- (1,1-Dimethyl-1'-2-propiones) / 3,5-dichlorobenzamic dmalcinic acid hydride,

3-Amino-1,2,3-triazole, mono-sodium ethanesone,

N, N-dimethyl-4, α-diphenylacetamide,

N, N-di (n-propyl) -2,6-dinicro-4-trifluoromethyl aniline,

N, N-di / n-propyl-2,6-triple tro-5-methylaniline,

N, N-di (n-propyl) -2,6-dinitr-1-methylsulfoxyl-ynyline,

O- (2,4-Dichloro-phenyl) -O-methyl-isopropylphosphoryl dothioate,

4-amino-3,5,6-trichloropicolinic acid,

2,3-dichloro-1,4-naphthoquinone, di (methoxythio carbonyl) diaulide,

3-isoprepyl-IR-2,1,3-benzothiadiazine / 4 / 3H-one 2,3-dioxide,

6.7-dihydrodipyrido [1,2-a]: 2,1-pyrazidium salts, 1'-di-ethyl-4,4-bipyridinium salts,

3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine

1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate,

N-sec-butyl-2,6-dinitro-3,4-xylidine,

N-sec-butyl-4-tert-butyl-2,6-dinitroaniline,

N ² , N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,

1,1,1-trifluoro- (4'-phenylsulfonyl) methanesulfone-o-toluidine,

2- (1-naphthoxy) -N, N-diethylpropionamide,

2-tert-butyl-4- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-5-one,

4-Chloro-5-methylamino-2- [lithium], (t-trifluoro-m-tolyl) -3 (2H) -pyridazinone,

N-cyclopropylmethyl-1,4,4-trifluoro-2,6-dinitro-N-proplyl-p-toluidine,

N-phosphonomethylglycine.

As plant growth regulators, for example, the following compounds may be combined with the herbicides of the invention:

maleic hydrazide and its salts,

9-hydroxyfluorene-9-carboxylic acid, its salts and esters,

2-chloro-9-hydroxyfluorene-9-carboxylic acid, its salts and esters,

1- (4-chlorophenyl) -1,2-dihydro-4,6-dimethyl-2-oxonicotinic acid and its salts,

4-methyl-3- (trifluoromethylsulfonyl) amidoacetanilide,

2,4-dimethyl-5- (1'-fluoromethylsulfonyl) amidoacetanilide.

When mixtures of herbicides are used, the relative amounts of the individual components depend on the crops to be treated, as well as on the type of weed weed.

Extending the usefulness of the herbicides according to the invention and the mixtures of herbicides can be achieved by the addition of substances which do not significantly reduce the desired effect but increase the tolerability of the active substances for the useful plants. Such substances are called antidotes.

For herbicides mainly used to control broadleaf weeds, the addition of certain carboxylic acid amides as antidotes has been proposed to improve their selectivity. Thus, for example, DOS No. 2,218,097 describes carboxylic acid amides as antidotes for a variety of herbicidally active thiocarbamates, acetanilides, triazines, and 2,4-dichlorophenoxyacetic acid. According to DOS No. 2,402,983, antidotes of the same type are suitable for improving the selectivity of the herbicidally active chloroacetanilides. Another class of alkanesulfonate-based antidotes for the protection of cereals using the herbicidally active thiolcarbamates and triazines is disclosed in DOS No. 2,141,586.

Another class of antidotes that can be used in combination with thiocarbamate herbicides is derived from 2,3-dibromopropionamide.

It has now been found that the known antidotes are surprisingly suitable also for improving the selectivity of the herbicidally active compounds of the general formula 1.

The invention thus also provides a method for the selective control of weeds, in particular maize, rice, wheat and other cereals, comprising applying an herbicide of formula X, optionally in admixture with other known herbicides, in combination with an antidote selected from the group consisting of and / or compounds of formula A

CHCl 2 -CO-N (A) in which

R _a represents a hydrogen atom, a straight or branched (C 1 -C 5) alkyl group which may be optionally substituted or substituted by a cyano or C 3 -C 6 cycloalkyl group, a (C 3 -C 6) alkenyl or alkynyl group or an optionally halogenated alkoxyalkyl group a dialkoxyalkyl or alkenyloxyalkyl group containing in each case not more than 6 carbon atoms, and

R 1 represents a straight or branched C 1 -C 5 alkyl group which may also be halogenated or substituted by a C 3 -C 5 cyano or C 3 -C 5 cycloalkyl, C 3 -C 5 alkylene or alkynyl group, optionally halogenated alkoxyalkyl, dialkoxyalkyl or an alkenyloxyalkyl group containing 1-6 carboxylic acid; in each case not more than δ of carbon atoms or a cycloalkyl radical of 3 to 6 carbon atoms, optionally substituted with ethenyl or ethynyl, or

R a _and R fc together with the nitrogen atom may also form a 5- to 7-membered heterocycle containing optionally an additional oxygen, nitrogen or sulfur atom and optionally substituted with one or more lower alkyl groups, b) compounds of formula B

BrCU ₂

-BrCH-CO-N (B) in which

R _c represents a hydrogen atom, an alkenyl group having a maximum of 5 carbon atoms or an alkyl group having a maximum of 5 carbon atoms, and

Rjj represents an alkyl, alkenyl or alkynyl group having in each case not more than 6 carbon atoms, a dialkoxyalkyl group having not more than 6 carbon atoms or a cycloalkyl radical having 3 to 6 carbon atoms, optionally substituted by an ethenyl or ethynyl group, or

R _c and R _c together with the nitrogen atom and optionally another nitrogen, oxygen or sulfur atom form a heterocycle optionally substituted by one or more lower alkyl groups, c / a compounds of formula C

Y- (CH ₂ ) _m -O-SO ₂ Q (C) wherein m is an integer of 1 to 6,

Q represents an optionally halogenated alkyl group having up to 6 carbon atoms, an acetoxy (lower) alkyl group, an acetoxy-halo- (lower) alkyl group or an aryl group, and

Y represents a chlorine or bromine atom,

These substances are applied in a conventional manner for antidotes. concurrently with the herbicide, the herbicide and the antidote being used in the form of co-formulations or sprayings prepared therefrom. However, the active ingredient and the antidote may also be used in the form of a mixture prepared before use in a reservoir. Separate application is also possible, in particular treatment of the agricultural area before or after sowing with antldot and then with herbicide. Finally, the application can also be effected by first applying the herbicide and shortly thereafter the antidote.

As compounds of formula A are preferred those compounds wherein R _a is an unsaturated residue, especially an allyl group and R represents an allyl, or propyl stylish. When R and R R together with the nitrogen atom form a heterocycle, the heterocycle is preferably a 2,2-diethyl-1,3-oxazole Vidinyl, pyrrolidinyl, piperidinyl or morpholinyl residue.

Preferred compounds of formula (B) are those in which R @ _c is hydrogen or even ethyl and allyl is a branched alkyl radical, in particular a target. butyl, isopropyl, 3-methyl-3-butynyl, 4-methyl-2-pentyl or allyl, 2,2-dimethoxyethyl, 2-ethylbutyl or 1-ethynylcyclohexyl.

Preferred antidotes of formula C are those wherein X is bromine, m is 2 or 3, and Q is methyl or ethyl.

Herbicides are applied in the same amount as proposed for their use without antidotes,

However, the improved tolerability due to the addition of an antidote allows the use of the herbicide in higher than usual amounts, which may be advantageous in that the use of higher amounts of herbicides may also affect those undesirable plants which otherwise cannot be sufficiently eradicated or conditions very unfavorable for the use of herbicides, where it is desired to achieve a more complete or certain effect.

The weight ratio of the antidote to the herbicide of the active compound is between 1:10 and 10: 1. preferably from 1: 6 to 2: 1 and especially from 1: 4 to 1: 1.

The active ingredients together with the antidotes are formulated into the appropriate formulations in a manner conventional in the art of herbicides using suitable excipients and carriers. Said compositions may take the form of, for example, suspendable powders, emulsion concentrates, granulates or dusts.

The following test demonstrates the efficacy of the compounds of the invention and combinations thereof with antidotes.

Corn seeds (Harrach grade) are sewn into plastic pots (12 cm diameter) filled with garden ground and covered with a layer of pure sand.

Immediately after sowing, the test preparations, or mixtures of herbicides with antidotes, are then applied in various concentrations and, in the case of mixtures, in different weight ratios, with the amount of water corresponding to 1,200 liters per hectare. The treated pots were then placed in a greenhouse where the temperature was maintained at 23 ° C during the day and 18 ° C at 2 ° C at night.

When the maize plants in the untreated control pots reach a height of 15 cm, both control and treated plants are cut off and weighed. The fresh weight is a measure of the herbicidal effect and is expressed as the effect in Z. From the curves obtained after plotting the effect against the dose, the effective doses (ED 10 - 50) can be determined.

The results obtained are summarized in the following table, which presents the results of two trials at tolerable dose limits of active substances and mixtures thereof with corn antidotes in kg of active substance per hectare.

herbicide antidotura ratio limit dose experiment 1 ED 30 Compatibility Experiment 2 ED 50 AND 0.2 0.4 X + A 1 - 1 0.9 - AND + A 1: 0.25 0.9 2,0 II 0.3 0.3 II + A 1 - 1 - 3.0 II + A 1: 0.5 1,2 3.0

I = 2- [4- (4-chlorophenoxymethyl) phenoxy] propionic acid

II = 2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid methyl ester

A from N, N-diallyldichloroacetamide

Addition of antidote A increases the tolerability limit of the herbicide by three to ten times.

The preparation of the active compounds according to the invention is illustrated by the following non-limiting examples.

He did

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid methyl ester a) A mixture of 45 g (0.37 mol) of 4-hydroxybenzaldehyde, 111 g (0.81 mol) of potassium carbonate, ml (0.81 mol) of methyl 2- of bromopropionic acid and 300 ml of dimethylformamide are heated to 60 ° C with stirring for 16 hours. The reaction mixture was then poured into 1 liter of water and extracted with ether. The ethereal solution was washed with 1N potassium hydroxide solution and water, dried and evaporated. The oily residue (55 g) can be purified by silica gel column chromatography using chloroform as eluent.

b) 44 g (0.211 mol) of 2- (4-formylphenoxy) propionic acid methyl ester was dissolved in 500 ml of methanol and 8 g (0.211 mol) of sodium hydride were added portionwise. The mixture was stirred at room temperature for 30 minutes and then at 60 ° C for 30 minutes, then evaporated in vacuo to half volume and poured into water. The aqueous mixture was neutralized with hydrochloric acid and extracted with ether. Washing, drying and evaporation of the extract gave 20 g of a colorless oil which was purified by silica gel column chromatography using chloroform as eluent.

(c) A solution of 12 g (0.058 mol) of methyl 2- (4-hydroxymethylphenoxy) propionate in 60 ml of hexamethylphosphoric triamide is cooled to -10 DEG C. and 4.4 ml / 0 is added dropwise thereto, 06 mol / thronylchlo198263 ridu. The reaction mixture was stirred at 0 ° C for 30 minutes and then at 10 ° C for 1 hour, then poured into water. After extraction with ether, the organic phase is washed with water, sodium bicarbonate solution and again with water; It is dried and the solvent is evaporated off under vacuum at room temperature.

d) 5.7 g (0.044 mol) of 4-chlorophenol and 10 g (0.044 mol) of ethyl 2- (4-chloromethylphenoxy) propionic acid ester were added to a solution of 1.01 g of sodium in 80 ml of ethanol, and the reaction mixture was stirred for 6 hours. with stirring under reflux. After evaporation of the solvent in vacuo, water was added to the residue and the mixture was extracted with ether. The ethereal phase is washed with 1N potassium hydroxide solution and water, dried and evaporated. The oily residue (11 g) was purified by silica gel column chromatography using benzene as eluent.

The oily ester initially crystallizes and melts at 76 ° C,

Example 2

2-C 4- (4-Chlorophenoxymethyl) phenoxy] propionic acid

A mixture of 6 g of the ester obtained according to Example 1, 5 g of potassium hydroxide and 60 ml of ethanol is refluxed for 2 hours. Water was added to the residue after evaporation of the solvent in vacuo and the solution was washed with ethyl acetate. The alkaline aqueous phase was acidified with dilute hydrochloric acid and the precipitated acid was extracted with ethyl acetate. The organic phase was dried and evaporated. 5 g of crystalline residue are obtained, which is stirred with hexane and filtered off with suction.

The yield of the product melting at 156-158 DEG C. is 3.8 g.

He did

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid ethyl ester a) Mixture of 34.8 g (0.37 mol) phenol, 111 g (0.81 mol) potassium carbonate, 89 g (0.69 mol) ethyl 2- of bromopropionic acid and 200 ml of ethanol are boiled under stirring for 12 hours, then filtered and distilled. 44.2 g of ethyl 2-phenoxypropionate having a boiling point of 93 DEG-94 DEG C./13 mbar are obtained.

b) To a suspension of 9.6 g of paraformaldehyde in 40 ml of concentrated hydrochloric acid under vigorous stirring, gaseous hydrogen chloride is introduced until a solution is formed. The temperature of the hydrogen chloride was maintained at 15-20 ° C. A solution of 38.8 g (0.2 mol) of 2-phenoxypropionic acid ethyl ester in 20 ml of benzene was added thereto, followed by stirring at 15-20 ° C for 4 hours. C, then 30 ml of benzene are added and the organic phase is separated. The organic solution is shaken three times with half-saturated aqueous sodium chloride solution, dried over sodium sulfate and the benzene is distilled off. The residue was distilled by erection distillation to give 18 g of the desired product, b.p. 134-138 DEG C./0.5 mbar.

c) Further treatment of the above product by treatment with 4-chlorophenol as described in Example 1 b) affords the title compound, m.p. 42 ° C.

Example 4 2- [4-Chlorophenoxymethyl / phenoxy] propionic acid n-butyl ester

A mixture of 6.4 g of the methyl ester prepared according to Example 1, 50 ml of n-butyl alcohol and 0.03 g of sodium was refluxed for 4 hours. The reaction mixture is left to stand overnight, the precipitate is filtered off with suction and the filtrate is evaporated to dryness in vacuo. After recrystallization of the residue from a mixture of water and ethanol, the title compound is obtained in a yield of 4.5 g (62%). .

An analogous procedure gives 2- [4- (3-chlorophenoxymethyl) phenoxy] propionic acid isobutyl ester, m.p. 75 DEG C. and 2- [4- (4-chlorophenoxymethyl) phenoxy] propionic acid n-amyl ester, m.p. 40 DEG C. .

Example 5

2- [4- (4-Chloro-phenoxymethyl) -phenoxyl-propionic acid ethyl ester g of sodium was dissolved in 4000 ml of ethanol and 2000 g of the methyl ester prepared according to Example 1 was added thereto, followed by refluxing for 0.5 h. a 10: 1 Teflux column is used to distill off a mixture of alcohols. After 3 hours, the alcohol is then distilled off directly, and finally the solvent is completely evaporated in vacuo. The residue is stirred at about 40 ° C with 2,000 rolls of toluene and the insoluble matter is filtered off at about the same temperature. The filtrate was completely freed of solvent under vacuum while heating in a boiling water bath and the residue was applied to a sheet. After cooling and scraping the metal sheet with a sharp object, the product starts to crystallize rapidly. Yield: 2 015 g (96.6% of theory);

Example 6 2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid isopropyl ester

6.1 g of 2- [4- (4-chlorophenoxymethyl) phenoxy propionic acid are dissolved in 50 ml of absolute tetrahydrofuran and 3.2 g of 1,1'-carbonyldiimidazole are added. The mixture was heated for a short time, then allowed to stand at room temperature for 4 hours, then 2.4 g of isopropyl alcohol was added. The reaction mixture was refluxed for 1 hour, then evaporated in vacuo on a rotary evaporator. The oily residue was recrystallized from a mixture of water and ethanol.

The yield of the product melting at 81 ° C is 4.5 g (65%).

The compounds listed in the following Table 1 are also obtained in an analogous manner:

Table 1

Compounds of Formula I (R = -COR ')

Compound No. R 'Melting point (° C)

-O-CH ₂ -CH ₂ -O-CH ₃ 58

-OC ₂ H ₅ 41

Example7

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid amide

6.4 g of the methyl ester prepared according to Example 1 are dissolved in 100 ml of ethanol under heating, 50 ml of concentrated aqueous ammonia solution are added and the mixture is gently heated in a water-bath to boiling. After the clear solution had formed, an additional 20 ml of ammonia solution was added until the turbidity began, and the mixture was refluxed for 30 minutes. After cooling, the crystalline product is filtered off with suction and washed with a mixture of ethanol and water. The yield of the product melting at 143 DEG C. is 3.5 g (57%).

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid 2-hydroxy-ethylamide, m.p. 111 DEG C., was also prepared in an analogous manner.

Example 8 2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid n-butylamide

6.4 g of the methyl ester prepared according to Example 1 are dissolved in 60 ml of methanol, 6.0 g of butylamine are added to the solution, and the mixture is heated in an autoclave under a pressure of 1.5 to 1.6 MPa for 4 hours.

After cooling, the solvent was distilled off in vacuo and the residue was recrystallized from ethanol.

The yield of the product melting at 98 DEG C. is 2.8 g (39%, theory).

Example9

2- [4- (4-Chlorophenoxymethyl) phenoxy] propionhydroxamic acid

To a solution of 1.4 g of hydroxylamine hydrochloride in 30 ml of methanol was added 20 ml of 1N sodium methoxide solution and the mixture was cooled in ice for about 5 minutes. The sodium chloride is filtered off with suction and the filtrate is added to a solution of 6.4 g of the methyl ester obtained in Example 1 in 30 ml of methanol. The mixture was shaken and an additional 20 mL of 1N sodium methoxide solution was added. The resulting mixture was allowed to stand overnight, then evaporated to about 10 ml in vacuo, the residue was taken up in water and acidified with 2N hydrochloric acid. The precipitated reaction product is filtered off with suction. The yield of the product melting at 142 DEG C. is 4.8 g (75% of theory).

t3

Example 10

2- (4- (4-Chloro-phenoxymethyl) -phenoxy) -propionhydroxamic acid methyl ester

The rydroxamic acid prepared according to Example 9 was treated with dimethyl sulfate at room temperature with the addition of potassium hydroxide. The title compound is recrystallized from toluene.

Yield: 68%, mp 114-11 ° C.

Example 11

2- (4- (4-Chloro-phenoxymethyl) -phenoxy] -ptopionic acid methyl ester)

6.1 g of 2- [4- (4-chlorophenoxymethyl) phenoxy] propionic acid are dissolved in 30 ml of water containing 0.96 g of sodium hydroxide, 3.02 g of dimethyl sulfate are added thereto, and after 10 minutes with stirring 0.3 g of bicarbonate sodium. The reaction mixture was stirred at room temperature for 6 hours, then left to stand overnight and was filtered off with suction. After drying, the residue is stirred with hot toluene and, after cooling, filtered. The solvent was distilled off in vacuo. The oily residue crystallizes upon cooling. The yield of the product melting at 76 DEG C. is 3.5 g (55% of theory).

Example 12

2- [4- (4-Chloro-phenoxymethyl) -enoxy] -propionic acid ethyl ester a) To a solution of 23 g (1 mol) of sodium in 400 ml of methanol is added 108 g (1 mol) of 4-methylphenol at room temperature. The solvent is then distilled off in a water pump vacuum. The residue is stirred with about 400 l of toluene, filtered and the filtrate is evaporated in vacuo. To a solution of the sodium salt thus obtained in 890 ml of tetrahydrofuran was added 181 g (1 mol) of ethyl 2-bromopropionate over 30 minutes with stirring, and the mixture was heated under reflux for 6 hours. . After washing with tetrahydrofuran, drying over sodium sulfate and evaporation in a water pump vacuum, 248 g of a light brown oily residue are obtained, which is distilled through a column in an oil pump vacuum.

201.5 g (96.7% of theory) of the product with a boiling point (8 DEG-82 DEG C.) of 15 l are obtained.

b) 20.8 g (0.1 mol) of 2- (4-methylphenoxy) propionic acid ethyl ester is dissolved in 60 ml of chloroform, the solution is heated to boiling and a solution of 6.8 ml / 0.125 mol is added over 2 hours. of bromine in 20 ml of chloroform. The mixture is irradiated with a 200-watt bulb with vigorous stirring. The rate of addition of bromine was controlled so that the reaction solution remained almost colorless. The reaction mixture was then allowed to react for a further 1 hour at boiling and then cooled to room temperature. The cooled solution was washed first with ice water, then with cold sodium bicarbonate solution and again with ice water. After evaporation drying, 31.5 g of a pale brown oily residue are obtained, which is fractionally distilled through a colossus under an oil pump vacuum.

Yield of the product boiling at 117-124 ° C / 19 ° and Sia 71 X theory.

Broraeci can also be performed as follows:

c) 17 g (0.08 mol) of ethyl 2- (4-methylphenoxy) propionic acid and 0.2 g of 2,2-aza-bis- (2-methylpropionitrile) are dissolved in 100 ml of chloroform, the solution is heated to boiling and a solution of 5.4 ml of bromine in 20 ml of chloroform was added thereto over 45 minutes. The mixture is then cooled to about 40 DEG C., 0.2 g of catalyst are added again and then the remaining portion of the bromine solution is boiled. The reaction mixture is allowed to react for a further 2 hours at the boiling point and is then cooled to room temperature. sodium sulfate. The solvent was distilled off under a water pump vacuum and the liquid residue was fractionally distilled under an oil pump vacuum.

Yield of the product boiling at 128-134 ° C / 27 Pa.

d) To a solution of 2.3 g (0.1 mol) of sodium in 100 ml of ethanol was added at room temperature

12.8 g (0.1 mol) of 4-chlorophenol. The resulting solution was allowed to react under boiling, and after cooling to room temperature, a solution of 28.7 g (0.1 mol) of ethyl 2- (4-bromomethylphenoxy) propionic acid in 20 ml of ethanol was added thereto with vigorous stirring. The mixture is heated to boiling for several hours, then cooled to room temperature and filtered off with suction through a pad of diatomaceous earth. The viscous residue after evaporation is stirred with 100 ml of isopropyl ether and suction filtered through a pad of diatomaceous earth. The filtrate was evaporated and the residue was distilled in a water pump vacuum.

The yield of the product boiling at 185-190 ° C / 13 Pa was 71% of theory.

Example 13

2- [4- (4-Chlorophenoxymethyl) phenoxy] propionic acid

To a vigorously stirred solution of 37 g of ground potassium hydroxide in 300 ml of ethanol was added a solution of 42.8 g (0.128 mol) of the ethyl ester prepared according to Example 12 in 60 ml of ethanol. The reaction mixture was reacted first at room temperature for 30 minutes and then at reflux for 3 hours. After evaporation of the solvent in vacuo, the residue is taken up in 300 ml of water and slightly acidified. diluted with hydrochloric acid. The precipitated product is filtered off with suction and washed with water and dried.

Yield: 37.3 g (96% of theory);

Example 14

2- [4- (4-Chloro-phenoxymethyl) -phenoxy] -propionic acid ethyl ester a) 24.8 g (0.2 mol) of 4-hydroxybenzyl alcohol, 39.8 g (0.22 mol) of 2-bromopropionic acid ethyl ester, 61 g / 0 44 mol / l potassium carbonate powder and 200 ml acetone were heated under reflux for 10 hours. The insoluble and precipitated fractions were filtered off with suction and the acetone was distilled off on a rotary evaporator. Rest the rest! Fractional distillation.

The yield of product boiling at 143-147 ° C (13 Pa) was 26.3 g (59% of theory), (b) 26 g (0.116 mol) of the compound obtained under a) and was dissolved in 100 ml of absolute toluene, the solution was cooled to -10 ° C and 8.3 ml (0.116 mol) of thionyl chloride are added dropwise with stirring at this temperature. The resulting mixture was stirred for 0.5 hour at 0 ° C and 1 hour at 10 ° C, then poured into 400 ml of water, the toluene layer was separated and the aqueous layer was shaken with 100 ml of ether. The organic phases are combined, shaken first with water, then with sodium bicarbonate solution and again with water, the organic solution is dried over sodium sulphate and the solvent is distilled off. Yield 26 g.

c) 2.5 g (0.11 mol) of sodium are dissolved in 100 ml of ethanol, 12.9 g (0.1 mol) of 4-chlorophenol are added thereto, and after about 5 minutes, 24.3 g / 0, 1 mol / mol of crude product obtained by the process of paragraph b). The reaction mixture is refluxed for 9 hours, then the precipitated sodium chloride is filtered off and the solvent is distilled off on a rotary evaporator. The residue was dissolved in ether, washed with water, 1N sodium hydroxide solution and again with water, dried over sodium sulfate and evaporated. The reaction product can be purified by fractional distillation.

The yield of the product boiling at 190-200 ° C (13 Pa) was 13 g (39% of theory).

Example 15

2- [4- (4-Chlorophenoxymethyl) phenoxy] propan-1-ol

To 2.0 g of lithium aluminum hydride was added 50 ml of absolute tetrahydrofuran, a solution of 16.04 g (50 mmol) of 2-L4- (4-chlorophenoxymethyl) phenoxy] propionic acid was added dropwise with stirring, and the resulting mixture was refluxed for 1 hour. The mixture is then allowed to cool and a mixture of 30 ml of tetrahydrofuran and 20 ml of water is added. Sufficient 2N hydrochloric acid was added to the thick suspension formed to dissolve the precipitated aluminum hydroxide and the solvent was distilled off in vacuo. The residue was recrystallized from aqueous methanol.

Yield: 12.1 g (83% of theory);

Claims (1)

SUBJECT OF THE INVENTION A herbicidal composition comprising, as an active ingredient, a compound of the formula (I ₎ - ( ₁₎ - ( ₁₎ - (OCH ₂ - ₎ - (O) - CH 2 R ₃ (1), in which: R is -CH ₂ Oli, -COOH, -COOKat, -COOR, -CONHj, -CONHOCH3 or -CONHCH2CH2OR wherein R 1 represents an alkyl group having 1 to 5 carbon atoms optionally interrupted by an oxygen atom and Kat is the equivalent of an inorganic or organic cation. Swroprsfig. n. p · xw.wl 1, Moet