DD145363A5 - HERBICIDE MEDIUM - Google Patents

Abstract

Substituted β-naphthol and β-Teirahydronaphthyl- phenyl ether of the formula wherein R is an optionally substituted by alkyl or halogen (Cl, Br) substituted ß-naphthyl or ß-Tetrahydronaphthylrest, R- | H or Aikyi, q is 0, 1 or 2 and Z is a carboxylic ester, thiocarboxylic, carbonic carbohydrazide, thioamide, nitrile, alcohol, aldehyde, acetal, oxime, carboxylate, carbamate or sulfonate group valuable selective herbicides. - Formula

Description

The invention relates to herbicidal compositions containing as active ingredient ß-naphthyl and ß-tetrahydronaphthyl-phenyl ether of the following general formula (I).

C har akteristik of the known technical solutions

It is known that β-naphthoxy-propionic acid derivatives have a selective herbicidal action against broadleaf weeds and are used especially for controlling unwanted plant growth in rice cultivation (JA-OS 125 740-76). As with all phenoxy and naphthoxyalkanecarboxylic acid derivatives / R. Wegler (ed.): Chemie der Pflanzenschutz- und Schädlingsbekungsmittel, Bd. 2 (1970), p. 276 ff J of the growth-factor type also lacks an activity against grassy weeds in these products.

Object of the invention

The compositions according to the invention are distinguished by a good herbicidal action against weed grass in the pre-emergence and post-emergence. Of the phenoxy-phenoxy-alkanecarboxylic acid derivatives known from DE-OS 22 23 894 and 26 01 548, the compounds used according to the invention differ by an additional, distinctly pronounced

- 1a -

54 241 18

Action against dicotyledonous weeds «

Even at high dosages, the funds are tolerated against many important crops. They are therefore suitable as selective herbicides in agricultural and horticultural crops. They can be combined with other herbicides, insecticides and fungicides.

Explanation of the essence of the invention

The object of the invention is to provide new herbicidal compositions,

The invention relates to herbicidal agents which are characterized by a content of a compound of general formula I.

R) -O

_0 -CH- (CH ₂₎ -Z

or

2 -

X = hydrogen or halogen,

Y = hydrogen, (C ₁ -C ₄ ) -alkyl or halogen

R ₁ = hydrogen or (C ₁ -C ₄ ) -alkyl,

Cf. = an integer from 0-2,

Z = a group of the formula -C-OR ₃ , -C-SR ₃ 0 R, Ο ^R 6 / ^R 7 S

Ii / ⁴ . il. / I

-CN, -CNN, -C -NH ₀ ,

TO R P

^K 5 ^K 8

^R 9

^HE 10

0 · OR.

Il \ / ⁴

CN, -CH ₀ OH, -C, -CH

Il \ /

CH ₀ -OCR ₁₁ , -CH ₀ -OCN or

R ₀ = H, (C ₁ -C ₁₂ ⁾ -alkyl, which is optionally substituted one to six times by halogen and / or by hydroxy, (C ₁ -Cg) -alkoxy, (C ₁ -C ₄ ) -alkylthio, (C , -Cg) -alkoxy (C ₂ -Cg) -alkoxy, halo (C ₁ -C ₃ ) -alkoxy, methoxy-ethoxy-sthoxy, (C ₁ -C 6 -alkylamino, di (C ₁ -C ₄ ) - Alkylaraino, phenyl, oxiranyl or phenoxy, the latter likewise being mono- to disubstituted by halogen and / or (C ₁ -C ₄ ) -alkyl, (C ₅ -C ₆ ) -cycloalkyl, halogeno (C ₅ -Cg) -alkyl, (C ₃ -Cg) -alkenyl, halogen- (C ₃ -Cg) -alkenyl, (C ₅ -Cg) -Cycolo-

-di

alkenyl, (C ₃ -C ₄ ) -alkynyl, which is optionally monosubstituted or disubstituted by (C ₁ -C 6) -alkyl, phenyl, halogen and / or (C ₁ -C ₂ ) -alkoxy, phenyl which is optionally one to three times by (C ₁ -C ₄ J-Al) CyI, (C ₁ -C ₄ ) -alkoxy, halogen, NO ₂

and / or CF _{3 is} substituted, furfuryl, tetrahydrofurfuryl or a cation equivalent of an organic or inorganic base;

R ₄ ⁼ (C ₁ -Cg) -AlkYl, which is optionally substituted by (C ₁ -C ₄ ) alkoxy, halogen or also mono- to trisubstituted by (C ₁ -C,) - alkyl and / or halogen-substituted phenyl , _f which is optionally monosubstituted to trisubstituted by (C ₁ -C ₄₎ -alkyl and / or halogen substituted (C ^ -CG) alkenyl or phenyl

is, R ₄ and R c are identical or different and H, (C ₁ -C ₄ ) -

Alkyl, hydroxy (C ₁ -C ₆ ) -alkyl, (C ₅ -C ₆ ) -cycloalkyl or phenyl, which is optionally mono- to trisubstituted by (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ J is substituted -alkoxy, halogen and / or CF, with the proviso that R ₄ and R are not commonly phenyl, mean or together form a methylene chain with 2, 4 or 5 members, in which a CH group can optionally ^ replaced by 0, NH or N (CH ₃ )

can be, .

R ₆ = H or CH ₃ , R ₇ = H, CH ₃ or C ₂ H ₅ , Rg = H, CH ₃ , C ₃ II ₅ or phenyl,

Rq and R ₁ are identical or different and are (C ₁ -C ₄ J -alkoxy, (C ₁ -C ₄₎ alkylthio, (C ₁ -C ₄₎ -alkylamino or di- (C ₁ -C ₄₎ alkylamino mean or together represent a radical of formula = NR ₁₂ ,

R ₁₁ =. (C ₁ -C 6) -alkyl, (C ₁ -C 6 -halogenoalkyl, C ₃ -, C ₅ - or C 6 -cycloalkyl, (C ₃ -C 6) -alkenyl, phenyl,

(C ₁ -C ₄ ) -alkylphenyl, (C ₁ -C ₄ ) -alkoxyphenyl, halophenyl, trifluoromethylphenyl, nitrophenyl or a radical of the formula

R ₁

^ Η-Ο-ζ ^ -Ο-

represents, as well

R ₁₂ = (C ₁ -C ₄ ) -alkyl or phenyl, which is optionally substituted by one to three times by halogen, CF ^, N0 ~ and / or (C ₁ -C ₄ ) -alkyl.

The alkyl mentioned in the radicals R ₁ -R _5, R ₁₁ and R _12, alkenyl and alkynyl radicals may be "." Includes both straight chain as well as branched halo "means preferably chlorine or bromine. The naphthyl (2) radical is preferably substituted or is substituted in the 1- or 1,6-position by Cl, Br or CH _2. Preferred as Z are the radicals -COOR ₂ , -CHpOH and -CH ₂ O-COR ₁₁ Cq = O) in which in turn R _{2 is} preferably alkyl or alkoxyalkyl or R _{11 is} alkyl The compounds of formula I are largely new, only the 2- / 4- (2-naphthoxy) phenoxy / propionic acid is from the DT-OS 2 136 828. Accordingly, the invention also relates to compounds of the formula I, with the exception of those in which R _{2 is} hydrogen,

The compounds of the formula I can be synthesized from starting materials which are known per se or prepared by known processes, by reacting compounds of the formula II.

C 0 - 0 ~ / V-OH II

or their alkali metal salts with compounds of the formula

l _IV

M-CH- (CH ₂ ) -Z or q '

in which R ₁ and Z have the abovementioned meanings and M is chlorine, bromine, mesyloxy or benzenesulfonyloxy optionally substituted in the aromatic ring, and if desired the resulting compounds of formula I by saponification, esterification, transesterification, salt formation, reduction, amidation , Acylation, dehydration, SuIfhydrierung, acetalization or Oxi.mbildung converted into corresponding derivatives of the formula I.

The reaction of II with III can be carried out in protic or aprotic solvents (eg water, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, hexamethylphosphoric triamide, "acetonitrile, acetone, methyl ethyl ketone, benzene, toluene, xylene" chlorobenzene, Dichlorobenzene), either the salts of the β-naphthoxyphenols being used or, when using the free phenols, by adding acid-binding agents for the capture of the resulting acids, the reaction times and reaction times required are largely determined by the solvents used ,

When reacting the free β-naphthoxy-phenols with haloalkanecarboxylic acid derivatives, aprotic dipolar solvents such as acetone, methyl ethyl ketone or acetonitrile can be used as reaction media. The use of alkali carbonates, especially sodium

ff / / t φ

or potassium carbonate, in equimolar amounts or a slight excess, as advantageous. The reaction is conveniently carried out at the boiling point of the particular solvent, the required reaction times are between about 3 hours and 30 hours. The structure of the phenol affects the reaction time and the choice of solvent to a considerable extent.

The described reaction procedure is also at Ein. Set of sulfonic acid ^ ^. As the mesylates or tosylates as Verätherungskomponente - especially when producing optically active preparations - preferred. In acetone, the reaction time can be up to 70 hours.

When using higher-boiling aprotic dipolar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone or hexa-methyl-phosphoric triamide temperatures below the respective boiling point are suitably chosen, since these solvents - especially in the presence of bases - at atmospheric pressure in part already boil with considerable decomposition. It is preferable to choose temperatures between 90 ° and 160 ° C, the reaction times are often only a few minutes to about 2-3 hours. Used as auxiliary bases in preferably equimolar ratios, alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide, are suitable in addition to the alkali metal carbonates.

When using the phenols in the form of their salts, for. As sodium or potassium phenolates, aromatic solvents such as benzene, toluene or xylene and chlorinated aromatics such as chlorobenzene or o-dichlorobenzene are suitable as reaction media. At temperatures of 8Q ° - 160 ⁰ C be

^ 5 in general reaction times between 1 and 6 hours

needed. The use of a base is not required in these cases.

According to the above methods, the largest number of the inventive ß-naphthyl-phenyl ether is directly accessible in good yields when using the corresponding synthesis components of the formula III. In special cases, it is necessary or advantageous to prepare the desired derivatives by secondary conversion of compounds obtained in the first stage. These secondary conversions take place with the aid of literature-restricted methods. Thus, free acids of the formula I (Z = -COOH) are subsequently converted into aldehydes (Z = -CHO), esters (Z = COOR ₂ ), salts (Z = -COOKat),

/ ^R 4 'R

Amides (Z = -CON ^ ^ _{hydrazides (z β} -coNRg-N (^) or

^{5 R} 8

Thiolester (Z - -COSR ₃ ) transferred; For this purpose, z is formed. B. from the free acids, first, the acid halides and

P ₀ reduces this with catalytically excited hydrogen

Rosenmund (> aldehydes) or sets the acid halides

with alcohols (> esters)} amines (> amides), hydra-

zinen (> hydrazides) or mercaptans (> thiolester)

around. If desired, the readily available acid esters (Z = -COOR ₂ ) can be saponified and the resulting acids converted into other functional derivatives in the above manner. Nitriles (Z = -CN) can be obtained by dehydration of amides (Z = -CONH ₂ ) by means of POCl ₃ or P ₉ O ₁ - and in turn converted with H ^ S in thioamides (Z = -CSNH ₂ ). From esters can be obtained by direct reaction with amines or hydrazines, the amides or hydrazides. Reduktio'n the ester with metal hydrides, eg. B. LiAlH ,, provides alcohols (Z '= -CH ₂ OH), which in turn with corresponding acylating agents in carbonyl

oc säureester (Z = -CH ₀ -O-COR ₁₁₎ carbamic acid ester

(Z = -CH ₀ -O-CO-N) or sulfonic acid

(Z = -CHp-OSOpR ₁ ρ) can be converted. Finally, from the aldehydes (Z = -CHO) by reaction with alcohols, mercaptans, primary or secondary amines whose acetals, mercaptans, Schiff bases or aminals

produce (Z = -CH}.

The ß-naphthyl-phenyl ether of the formula X in all cases in which R. is H f, racemates, that is optically inactive mixtures of two enantiomeric (optically active =)

Components with opposite directions of rotation, where the carbon atom between 0 and * represents the center of the chirality, it was surprisingly found that the D-enantiomers are particularly herbicidally effective. The present invention therefore relates

both the optically inactive racemates and the optically

active enantiomers, in particular their D-form.

* (CH ₂ ) _q

The optically active isomers of the formula I are obtained, for example, by reacting as starting materials of the formula III

uses optically active compounds whose chi.rales

Center is adjacent to the rest of M. ,

The entantiomeric forms of the compounds of formula I

are further by cleavage of the racemates in their antipodes 30th

accessible using optically active excipients. To carry out this procedure, the derivatives are converted into a form suitable for separation, in most cases into the free acids.

54 241 18 -40-

Guidance to the starting derivative or other desired derivatives is possible by known chemical methods.

The agents generally contain the active ingredients of the formula I to 2 to 95 wt .-%. They can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.

Wettable powders are in V / asser uniformly dispersible preparations, in addition to the active ingredient except a diluent or inert or wetting agents, eg polyoxäthylierte alkylphenols, polyoxäthylierte oleyl, stearylamines, alkyl or AXkylphenyl sulfonates and dispersants, eg lignosulfonate, 2.2 '-dinaphthylmethane-6,6 ^f -disulfonsäures sodium or oleylmethyltaurine acid.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or even higher

r- 44 · * ·

boiling aromatics and addition of a nichtioni.schen wetting agent, such as a polyoxäthylierten alkylphenol or a polyoxäthylierten oleyl or stearylamine obtained

 5

Dusts are obtained by grinding the active ingredient with finely divided, solid substances, eg. Talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth

 10

Granules can be prepared either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, eg. As polyvinyl alcohol, sodium polyacrylate, or mineral oils on the surface of carriers, such as sand, kaolinites, or granulated inert material. Also, suitable agents may be used in the manufacture of fertilizer granules

conventional manner - if desired, mixed with fertilizers - produced.

In the herbicidal compositions, the concentrations of the active ingredients in the usual formulations may be different. In wettable powders, the drug concentration ζ varies. B. between about 10% and 95%, the remainder consists of the above-mentioned formulation additives. For emulsifiable concentrates, the drug concentration is about 10% to 80%. Contain dusty formulations

54 241 18

usually 5 to 20 % of active ingredient, sprayable solutions about 2 to 20 % _a In the case of granules, the active ingredient content Ze T depends on whether the active compound is liquid or solid and which granulating agents, fillers, etc. are used.

For use, the commercial concentrates are optionally diluted in a conventional manner, e.g. for wettable powders and emulsifiable concentrates by means of water. Dusty and granulated preparations and sprayable solutions are no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity and the like. the required application rate varies. It can vary within wide limits, eg. B. between 0.05 and 10.0 kg / ha or more active substance, but it is preferably between 0.1 and 5 kg / ha.

F inancial S e ttin gs I Herst l.lun g sbe i s ρ i e 1 e

Me inventive compounds are often highly viscous oils difficult to distill. For identification purposes, the NMR data are listed in Table 2 for these products. "For solid substances, the melting point is given.

In a hot 100 ° C stirred suspension of 26.8 g (0.1 mol)

54 241 18

dry sodium 4- (2-naphthoxy) phenolate in 100 ml of xylene are added dropwise in 15 minutes 12.3 g (0.1 mol) of 2-chloropropionic acid methyl ester. At the end of the addition, the temperature is raised slowly to 14O ⁰ C and

-ta-

-K-

then heated to boiling for 5 hours under reflux. After cooling, the resulting sodium chloride is separated by shaking the xylene phase with water; The solvent is removed by distilling off and the residue is fractionated under high vacuum.

There are obtained 29.6 g (92% of theory) of 2- / 4- (2-naphthoxy) -phenoxy_7 "propionic acid methyl ester, mp. 91 ° to 93 ° C.

OCH-COOCH ₃

Example 2:

2- / 4- (2-Napbthoxy) -pbenoxyZ-propionic acid-isob-gtylester

A mixture of 1.1.8 g (0.05 mole) of 4- (2-naphthoxy) phenol, to, 5 g (0, 0.5 mole) of isobutyl 2-bromopropionate and 6.9 g (0.05 mole) of powdered Anhydrous potassium carbonate is refluxed in 1OQ ml of acetone for 18 hours. After receiving sucks from the resulting potassium bromide / Kaliiiinhydrogencarbonat-salt mixture, the acetone is removed by distillation and receives as. Residue 16.9 g (93% of theory) of 2- (4-naphthoxy) -phenoxy-7-propionic acid isobutyl ester. By distillation in a high vacuum or by chromatography, the crude product can be purified

 KMR data s. Table 2 «

CH ₀ CH ₀ , 3, 3

0-CH-COOCH ₀ CH

CH ₃

Example 3:. '

2- / 4- (1-chloro-2-naphthoxy) -propionic acid ethyl -phenoxyy-

ester

A mixture of 16.3 g (0.060 mol) of 4- (1-chloro-2-naphthoxy) phenol, 11.4 g (0.063 mol) of 2-bromopropionic acid ethyl ester and 8.7 g (0.063 mol) of powdered Anhydrous potassium carbonate is refluxed in 100 ml of acetone for 30 hours. After cooling, the mixture is filtered off with suction from the resulting potassium bromide / potassium bicarbonate salt mixture. The residue remaining after evaporation of the solvent is taken up in chloroform and filtered through a silica gel layer for purification.

After removal of the chloroform by distilling off, 20.6 g (93% of theory) of ethyl 2- / 4- (1-chloro-2-naphthoxy) phenoxy-propionate are obtained. NMR data s. Table 2.

CH,

ΓΛ

0-CJI-COOC ₂ H ₅

Example 4:

D - (+) - 2- / 4- (2-naphthoxy) -phenoxy-Z-propionic acid ethyl r

A mixture of 11.5 g (48.7 mmol) of 4- (2-naphthoxy) -phenol, 13.7 g (50.4 mmol) of L - (-) - lactic acid ethyl ester tosylate and 7.4 g (53.6 mmol) of powdered anhydrous potassium carbonate is refluxed in 80 ml of acetonitrile for 25 hours. After cooling, the mixture is filtered off with suction from the resulting potassium toluenesulfonate / potassium bicarbonate salt mixture, the solvent is removed by evaporation and the crude ethyl D- (+) -2- / 4- (2-naphthoxy) phenoxy / propionate is purified after absorption in ethylene chloride Chromatograph on silica gel. This gives 12.9 g (7 9% of theory) of purified product

2 5

a rotation of / «x / p = 18.4 ° (1 m in chloroform) as a non-crystalline substance

 NMR data s. Table 2.

COOC ₂ H ₅

t -eS3 0 CH ₃

Example 5:

2- / 4- (T-methyl-2- naphthoxy) -pheoxypropionic acid · · ·

16.8 g (5OmMoI) of 2- / 4- (1-methyl-2-naphthoxy) phenoxy_7-propionic acid methyl ester (Example 36) are dissolved in 100 ml of methanol and saponified by adding 200 ml of 2N sodium hydroxide solution in the boiling point. Distilling off the methanol and acidifying provide 15.4 g of 2- / T- (1-methyl-2-yl)

naphthoxyl-phenoxy _ / - propionic acid, mp 112-7 ⁰ C..

O - (()) - OCHCOOH

Example 6: 15 2- / 4- (2-Naphthoxy) -phenoxy- YZ-propionamide

30.8 g (0.01 mol) of 2- / 1- (2-naphthoxy) -phenoxy-7-propionic acid (Example "60) are dissolved in 200 ml of benzene and, after addition of 14.3 g (0.12 mol) of thionyl chloride By distilling off the excess thionyl chloride and the benzene, 32.7 g of crude acid chloride are obtained, which is dissolved in 60 ml of toluene and added dropwise at room temperature to an ammoniacal toluene solution Initiation of ammonia for 2 hours, the last being heated to about 80 ^° C. After cooling off, the precipitate which has been precipitated is filtered off, washed with water and dried, giving 24.3 g (83% of theory) of 2- I- (2-naphthoxy) -phenoxy_7-propionamide, mp. 147-148 ⁰ C. from the filtrate may be recovered a further fraction of 3.6 g (12%) of product.

CH,

OCH-CONH,

Example 7:

2- / 4- (2-naphthoxy) -phenoxy / -n-propano_l

A solution of 32.2 g (0.1 mol) of methyl 2- / T- (2-naphthoxy) phenoxy / propionate (Example 1) is dissolved in 100 ml of tetrahydrofuran and dissolved within 1.5 hours.

the dripped to a heated to 65 ° C suspension of 3.8 g (O, 1 mol) of lithium aluminum chloride in 50 ml of tetrahydrofuran. Then heated for 1 hour to boiling under reflux, then cooled and dripped to decompose the excess lithium aluminum hydride 2O ml of ethyl acetate, then 60 ml of water. After acidification with sulfuric acid and separation of the aqueous phase, the tetrahydrofuran is evaporated off, the residue is taken up in chloroform, washed with water, dried and the solvent is removed. This leaves 24.8 g (84% of theory) of 2-1- (2-naphthoxy) -phenoxv-7-n-propanol, ρ = 1.6173.

OCH-CH ₂ OH

Example 8 '

2- / 4- (2-Naphthoxy) -phenoxyZ-n-propyl-chloroacetate

10.0 g (34 mmol) of 2- / 4- (2-naphthoxy) -phenoxy / -n-propanol are dissolved together with 4.0 g (40 mmol) of triethylamine in 50 ml of toluene. To this solution is added dropwise within 4 0 min at room temperature, a solution of 4.2 g (37 mmol) of chloroacetyl chloride. After the addition is complete.

Heated to 100 ⁰ C for 6 hours. After cooling, the resulting triethylammonium-H-ydrochloride precipitate is filtered off with suction and the filtrate is washed with 2N hydrochloric acid and water. The toluene solution is filtered through 50 g of silica gel; the solvent is distilled off under reduced pressure to give 10.7 g (85% of theory)

2- / 4- (2-naphthoxy) -phenoxy_7-n-propyl-chloroacetate

20 · non-crystalline substance, n _Q = 1.5980.

OCH-CH ₂ OC-CH ₂ Cl

N-methyl-O- (2-4- (2-naphthoxy) -phenoxyZ-n-propyl) -

carbamate 30

10.3 g (35 mmol) of 2- / J- (2-naphthoxy) -phenoxy-7-n-propanol

are dissolved in 50 ml of toluene and after addition of 2 ml of triethylamine with 2.2 g (39 mmol) of N-methyl isocyanate at room temperature. The mixture is heated to 100 ⁰ C within one hour and stirred at this temperature for 6 hours. After cooling, it is washed with 100 ml of toluene

10

diluted and then washed with 2 η hydrochloric acid and water. Drying and evaporation of the solvent provides 11.7 g (95% of theory) of N-methyl-O- {2- / 4- (2-naphthoxy) -phenoxy_ / -n-propyl-V-carbamate as not

crystalline substance »* = 1.5981.

CH,

CH-CH ₂ OC-NHCH ₃

Example 10

2- / 4- (2-Naphthoxy) -phenoxy-Z- propionitrile

2.0 g (6.5 mmol) of 2- (4- (2-naphthoxy) -phenoxy) -propionamide are dissolved in 30 ml of toluene with heating and, after addition of 9.6 g (8.0 mmol) of thionyl chloride Refluxing the unreacted thionyl chloride and the toluene, the residue is taken up in 260 ml of chloroform and filtered through 20 g of silica gel. 96% of theory) 2- / T- (2-naphthoxy) -phenoxy_7-propioni tril of mp. 93-94 ° C.

30

h ψ - ta - it-

Example 11

2- / 4- (1-chloro-2-naphthoxy) phenoxy / propionic acid ~ 2-methoxyethyl ester

14/3 g (40 mmol) of 2- / 4- (1-chloro-2-nap] ± hoxy) phenoxy_7 ~ propionic acid methyl ester (Example 39) are dissolved in 150 ml of ethylene glycol monomethyl ether in the presence of 1 ml of conc. Sulfuric acid for 7 hours at 100 ⁰ C heated, wherein

10, the methanol is distilled off constantly.

The excess ethylene glycol monomethyl ether is removed by distillation under reduced pressure, the residue is taken up in chloroform and washed with water until acid-free. After evaporation of the solvent remain

15.6 g (97% of theory) of 2- / T- (i-chloro-2-naphthoxy) -

phenoxy_ / -propionic acid 2-methoxy-ethyl ester as non-

20 crystalline substance with η = 1.5872.

j. Example 12

Sodium salt of 2- / 4- (1-bromo-2-naphthoxy) -phenoxy / -propionic acid

9.0 g (23.3 mmol) of 2- 4- (1-bromo-2-naphthoxy) -phenoxy-7-propionic acid (Example 71) are dissolved in 70 ml of ethanol and treated with 3.5 g of a 27% aqueous solution Sodium hydroxide solution (23.6 mmol) was added. The sodium salt of 2- / 4- (1-bromo-2-naphthoxy) phenoxy is distilled.

35 propionic acid with a mp of 170 ⁰ C.

Br CH ₃

O - /] \ OCH-COONa

Example 13

2- / 4- (2-naphthoxy) -phenoxyZ-acetic acid

24.9 (79 mmol) of 2- / 4- (2-naphthoxy) -phenoxy-1-acetic acid sodium salt (Example 58) are suspended in 250 ml of 2 N sulfuric acid. By heating for 15 min to 90 ⁰ C, the salt is converted into the free acid. Obtained by suction 23.4 g (100%) of 2- / T- (2-naphthoxy) phenoxyacetic acid, mp. 142.5 - 143 ° C.

0- (( Tv-OCH ₂ COOH

Example 14

2- / 4- (2-Naphthoxy ) -phenoxyZ- propionic acid-propargyl ester

13.2 g (43 mmol) of 2- / 4- (2-naphthoxy) -phenoxy-7-propionic acid (Example 60) are dissolved in 100 ml of benzene and after addition of 6.1 g (52 mmol) of thionyl chloride by 8 hours Heat to reflux under reflux into the acid chloride. By distilling off the excess thionyl chloride and benzene, 14.0 g of crude acid chloride are obtained. This is dissolved in 30 ml of toluene

dissolved and added dropwise at room temperature in 30 minutes to a solution of 2.9 g (52 mmol) of propargyl alcohol and 6.5 g (65 mmol) of triethylamine in 30 ml of toluene. The mixture is refluxed for 2.5 hours, filtered off with suction from the precipitate after cooling and the filtrate is washed with water. After drying and evaporation of the solvent, 12.8 g (86% of theory) of 2- / 4- (2-naphthoxy) -phenoxy_ / -propionic acid-propargyl ester,

20 n "= 1.5915. Any traces of the free acid will be filtered through. a solution of the ester in chloroform over silica gel.

20 Example 15

2- / 4- (1-Bromo-2-naphthoxy) -phenoxy / -propionic acid-2- chlorocyclohexyl ester

29.0 g (75 mmol) of 2- / 4- (1-bromo-2-naphthoxy) -phenoxyj / -propionic acid (Example 71) are dissolved in 150 ml of toluene. 10.6 g (75 mmol) of 2-chloro-cyclohexanol and 0.5 ml of conc. Sulfuric acid and heated for 4 hours to boiling under reflux, the resulting water is separated via a water.

After cooling and dilution with 100 ml of toluene is washed neutral with water and, after drying over sodium sulfate, the toluene distilled off. There remain 30.4 g (80% of theory)

NMR spectrum: s. Table 2

OCH-CO-O

Cl

φ G © r -> β - as-

Example 16

4- / 4- (2-naphthoxy) -phenoxyZ-n-butyric acid

Prepare by heating 23.6 g (0.10 mol) of 4- (2-naphthoxy) -phenyl with 50 ml of 2N sodium hydroxide solution (0.10 mol) in 100 ml of dibutyl diglycol ether at 120 ⁰ C, the sodium salt of the 4th - (2-naphthoxy) -phenol forth; then the water present is distilled off. Are added 9.5 g (0.11 mol) ^ -Butyrolacton and heated for 6 hours at 150 ⁰ C. The dibutyl diglycol ether is distilled off under reduced pressure and the residue taken up in water with warming. Acidification gives the 4- / 4- (2-naphthoxy) -phenoxy - / - n-

 J5 butyric acid.

^ r ^^ x - ^ / O \)) - OCH ₂ CH ₂ CH ₂ COOII

20

Example 17

4- / 4- (2- naphthoxy) phenoxy / -n-valeric acid

According to the procedure of Example 16, the compounds of using 11.0 g (0.11 mol) / 'valerolactone by 6 - hours of heating to 180 ⁰ C.

In an analogous manner, the following compounds are obtained using appropriate starting materials:

Table 1

I Example no. Θ ^R 1 J - (CH ₂ J _q - _Z Phys. dates table 2 made according to example 18 2-naphthyl H COOC ₂ H ₅ S. 2 19 2-naphthyl H CH ₂ CH ₂ COOC ₂ H ₅ table 2 2 20 2-naphthyl CH ₃ COOC ₂ H ₅ S. table 2 2 21 2-naphthyl CH ₃ COO-nC ₃ H ₇ S. table 2 2 22 2-naphthyl CH ₃ COO-IC ₃ H S. 2 23 2-naphthyl CH ₃ COOCH ₂ CH ₂ Cl. 2 24 2-naphthyl CH ₃ COOCH ₂ CH ₀ CH (OCH ₃ ) CH ₃ 2 25 26 2-naphthyl 2-naphthyl CH ₃ CH ₃ COOCH-O CH ₂ CH ₂ COOCH ₃ NJ NJ 27 2-naphthyl CH ₃ CONH ₂ 6 28 2-naphthyl CH ₃ CON (CH ₃ J ₂ 6 29 2-naphthyl CH ₃ CON (C ₂ H ₅ J ₂ 6 30 2-naphthyl CH ₃ CHO 31 2-naphthyl CH ₃ CS-NH ₂   ' 32 2-naphthyl CH ₃ COONH ₄ 12 33 2-naphthyl CH (CH ₃ ) 2 COO-XC ₃ H ₇ table 2 2 34 5,6,7,8-tetra CH ₃ ZOOCH ₃ S. 2 hydro-2- naphthyl

Table 1: (continued)

Example no. Θ ^R 1 COO-IC ₄ H ₉ Phys. dates made according to example 35 5,6,7,8-tetrahydro-2-naphthyl CH ₃ COOCH ₃ s. Table 2 2 36 1-methyl-2-naphthyl · CH ₃ . COO-IC ₄ H ₉ s. Table 2 2 37 1-methyl-2-naphthyl CH ₃ CH ₂ CH ₂ -COO-IC ₃ H ₇ s. Table 2 2 38 1-chloro-2-naphthyl H COOCH ₃ 2 39 1-chloro-2-naphthyl CH ₃ COO-IC ₄ H ₉ s. Table 2 2 40 1-chloro-2-naphthyl CH ₃ COO-Ii-C ₆ H ₁₁ s. Table 2 2 41 1-chloro-2-naphthyl CH ₃ COO-IC ₅ H ₁₁ s. Table 2 2 42 1-chloro-2-naphthyl CH ₃ CON (CH ₃ J ₂ s. Table 2 2 43 1-chloro-2-naphthyl CH ₃ CH ₂ OCOCHCl ₂ s. Table 2 6 44 1-chloro-2-naphthyl CH ₃ CH _o 0C0C _c H _c ί OD 8th 45 1-chloro-2-naphthyl CH ₃ COO-IC ₄ H ₉ 8th 46 1-chloro-2-naphthyl CH (CH ₃ J ₂ COOCH ₃ 2 47 1-bromo-2-naphthyl CH ₃ COO-IC ₄ H ₉ n _D ²⁰ : 1.6160 2 48 1-bromo-2-naphthyl CH ₃ CH ₂ CH ₂ COOC ₂ H ₅ n _D ²⁰ : 1.5875 2 49 1-bromo-2-naphthyl CH ₃ CO-NHC, H_O D 2 50 1-bromo-2-naphthyl CH ₃ COOCH ₃ 6 51 6-bromo-2-naphthyl CH ₃ COO-IC ₄ H ₉ s. Table 2 2 52 6-bromo-2-naphthyl CH ₃ s. Table 2 2

Table 1: (continued)

Example (R) 6-bromo-2-naphthy1 R ₁ - (CH ₀ ) -Z COOK Phys. dates manufactured No. 1,6-dibromo-2-naphthyl I Δ q COOC ₂ H ₅ to 1,6-Dibrora-2-naphthy1 COOCH ₃ - example 53 1,6-dibromo-2-naphthyl CH ₃ COO-IC ₃ K ₇ Fp.140-150 ° (dec.) 12 54 1,6-dibromo-2-naphthyl H CH ₂ CH ₂ COOCH ₃ 2 55 2-naphthyl CH ₃ COONa Fp.103-105 ° C 2 56 Il CH ₃ ^c ° -O n _D ²⁰ : 1.5940 2 57 Il CH ₃ COOK 2 58 Il H COO CH ₂ CHClCH ₂ Cl Mp> 250 ° (decomp.) 12 59 Il CH ₂ CH ₂ OCOCCl ₃ Fp.62-67 ° 6 60    II CH CH ₀ CH ₀ OCOC, .H.Cl (p) IZ 6 4 Mp 138 ° 5 61 1-methyl-2-naphthyl i It COO-NH ₂ (CH ₃ ) ₂ η ²⁰ : 1.5968 9 η 11 62 · 11 It CONHC ₆ H ₄ Cl (P) n _D ^TO: 1.5938 8th 63 1-chloro-2-naphthyl It COOH Fp.75-79 ° 8th 64 1-chloro-2-naphthyl Il COONa oil 12 65 ti ti COO <Hj s. Table 2 · 6 66 I i H CONHC ₅ H ₅ Mp 126.5-127 ° 5 67 Il Mp> 250 ° (decomp.) 12 68 II n _D ²⁰ : 1.5581 14 69 Il s. Table 2 6

Table 1: (continued)

Example no. Θ ^R 1 - <CH ₂ ) _q -Z COOH Phys. dates made after - 5 COOH example 5 70 1-chloro-2-naphthyl CH ₃ CONH-ZqV-ei s. Table 2 6 11 Cl CON (CH ₃ J ₂ CON (CH ₂ CH = CH ₂ ) ₂ 6 6 71 1-bromo-2-naphthyl ft Fp.109-115 ° 72. 6-bromo-2-naphthyl It Fp.127 ° 73 tt Il s. Table 2 74 75. 11 It It ti n _D ²⁰ : 1.6125 n _D ²⁰ : 1.608

Table 2:

60 MHz 'H-NMR data for the characterization of individual compounds from the series of preparation examples

Chemical shift (/ "/ ppm ?, relative to TMS as internal standard, in CDCI3 (in parentheses multiplicity and relative intensity of the signals)

Example] no.

CH.

.-CH

-OCH3

-OCHo-

-OCH

AROMAT

0.85 (d, 6) T, 65 (d, 3)

1.25 (t, 3) 1.65 (d, 3)

1.25 (t, 3) 1.65 (d, 2)

• 1.30 (t, 3)

1.30 (t, 3) 1.70 (d, 3)

0.95 (t, 3) 1.75 (d, 3)

_f 10-1.45 (2d, 6) 1.70 (d, 3)

1.60 (d, 3)

0.90 (d, 6) 1.60 (d, 3)

1.70-1.90 (m, 4) 2.70 (wide, m, 4)

1.60-1.90 (m, 4) 1.95 (m, 1) 2.70foreit, m, 4)

1, 90 (sept., 1)

3.75 (s, 3)

 3.95 (d, 2) 4.20 (q, 2) 4.25 (q, 2)

4.25 (q, 2) 4.55 (s, 2)

4.25 (q, 2) 4.20 (t, 2)

3.95 (d _r 2)

4,90 {q, 1) 4,70 (q, 1) 4,75 (q, 1)

4,80 (q, 1) 4,80 (q, 1) 4,70 (q, 1) 4,75 (q, 1) 4,75 (q, 1)

6.95-7.90 (m, 11);

6.70-7-95 (m, 9) 8.15-8.45 (m, 1)

6.75 to 7.95 (m, 11)

6.80 to 7.95 (m, 11)

6.80 to 8.05 (m, 11)

6.80 to 8.05 (m, 11)

6.80 to 8.05 (m, 11)

6.60 to 7.30 (m, 7)

6.60 to 7.30 (m, 7)

Table 2

(Continuation)

Example no.

CH.

-CH--

-CH-

-OCH

-OCH ₂ -

-OCH

aromat.

36 37

39 40 41 42

51 52

43 65 69

1.55 (d, 3) 2.50 (s, 3)

0.90 (d, 6) 1.55 (d, 3) 2.55 (d, 3)

1.60 (d, 3)

0.80 (d, 6) 1.60 (d, 3)

0.60 to 2.00 (m, 12)

0.65 to 1.95 (m, 13)

1.60 (d, 3)

O., 85 (d, 6) 1.60 (d, 3)

1.6 (d, 3) 3.0 (d, 6)

1 ₇ 5-1.7 (d, 3) 2.55 (s, 3)

1/6 (d, 3)

3.70 (s, 3)

'1,90 (sept., 1) \

3.80 (s, 3)

1.90 (sept., 1)

1.95 (± set., 1)

3.80 (s, 3)

.3,90 (d, 2)

3.90 (d, 2)

4.20 (t, 2)

4.70 (q, 1)

4.70 (q, 1)

4.70 (q, 1)

4.65 (q, 1)

4.70 (q, 1)

4.20 to 5.25 (m, 2)

3.95 (d, 2)

4.75 (q, 1)

4.70 (q, 1) 4.9 (q, D

4.75 (q, 1) NH: 3.75 (s, 1)

4.5-5.0 (q, 1)

NH: s, 1

6.75 to 8.10 (m, 10)

6.75 to 8.10 (m, 10)

6.80-8.00 (m, 9) 8.10-8.40 (m, 1)

6,60-7,90 (m, 9) 8,00-8,35 (111,1)

6.75-7.95 (m, 9) 8.15-8.50 (m, 1)

6.70-8.00 (m, 9) 8.15-8.45 (m, 1)

6.70 to 7.95 (m, 10)

6,70-7,90 (m, 10) 6,9 -8,4 (m, 10)

6.75-8.3 (ra, 14) 6.6 -8.4 (m, 15)

Table 2 (continued)

Example no. 1 -CH ₃ -CH-- -CH- -OCH ₃ ί -OCH ₂ - -OCH 6 TT aromat. 13) 70 1 , 6 (d, 3) 4.75 (q, 1) NH: 4.5 (s, 1) 6 8 , 4 to 8.4 (m, 9), 1) 15 , 6 (d, 3) 1, 0-2.5 (wide, m _r 8) 4-75 (q, 1) 3.5-4.3 (1) 4.5-5.1 (1) 7 , 7-8.0 (m,, 2-8.45 (m 10) 73 (1.0-2.4 m, 13) 4.5-5.0 (m, 2) .0-8,0 (m,

gh

& - 33 -

FORMULATION EXAMPLES Example A:

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient

75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol (10 AEO) as

Emulsifier.

Example B: ·

A wettable powder readily dispersible in water is obtained by reacting

25 parts by weight of active ingredient

64 parts by weight of kaolinhaltigen, quartz as inert material

10 parts by weight lignosulfonic acid potassium

and 1 part by weight of oleylmethyltaurine sodium as

'Wetting and dispersing agent

mixed and ground in a pin mill.

Example C:

A dust is obtained by

10 parts by weight of active ingredient • and 90 parts by weight of talc mixed as an inert material and comminuted in a hammer mill.

Example D ;

A granulate consists e.g. from about 2-15 parts by weight of active ingredient

98-85 parts by weight of inert granule materials, e.g. 35 attapulgite, pumice, and quartz sand.

BIOLOGICAL EXAMPLES Example I:

Compounds of the invention were sprayed onto flower pots after sowing weeds and subsequently observed for their herbicidal effectiveness and visually scored. The Bonitierung took place after the scheme of BOLLE (message sheet of the German plant protection service 16, 1964, 92-94):

value number 97 We weeds % in crops 0 1 95 100 to> 2.5 2 90 , 5 to <100 0 to> 5 t 3 85 to <. 97.5. 2.5 to> 10 4 75 to <95 5 until> 15 5 65 to <90 10 until> 25 6 32 to <ς85 15 to ^ 35 7 0 to <75 25 to> 67.5 8th , 5 to <65 35 up to> 100 9 to <32.5 67.5

The results in Table Ia show that the substances have very good herbicidal properties and fight many weeds well. ,

Similarly, many crops were seeded in pots and treated before emergence with the compounds of the invention. It was found that even high doses of 2.4 kg AS / ha caused no or only minor damage to the crop. The assessment took place about 4 weeks after application of the compounds. The results are listed in Table Ib. The experimental pots were kept under greenhouse conditions.

in the form of aqueous dispersions of wettable powder concentrates

Example II:

Various weeds and crop plants were sown in pots and grown in the greenhouse for about 3 weeks to the size of 15 to 25 cm. Subsequently, the plants were postemergence treated with the compounds of the invention. The visual assessment done about 4 weeks after application showed that weeds are well-controlled by the compounds, i. were killed while many crops were not or were negligibly damaged (see Table II).

Table Ia:

Herbicidal pre-emergence action against weeds and weeds

Connection according to example Dose kg AS / ha ALM SAL LOM ECG AMR 1 2.4 0.6 1 2 1 2 1 .1 1 1 - 20 2.-4 0.6 1 2 1 3 1 1 1 2 2 3 21 2.4 0.6 1 2 1 2 1 1 1 1 - 22 2.4 0.6 Ί 1 1 2 1 2 1 1 1 3

ALM = Alopecurus myosuroides SAL = Setaria lutescens LOM = Lolium multiflorum ECG = Echinochloa crus galli AMR = Amaranthus retroflexus AS = Active substance

Table Ib:

Tolerance of important crops in pre-emergence

Connection according to example Dose kg AS / ha Peanut Soybean Bean Broad bean tobacco wheat alfalfa rape 1 20 21 2,4 2,4 2,4 2 1 1 CO CO CO 3 2 3 1 1 2 4 1 2 2 5 3 2 4 4 1 2

Table II:

Post-emergent herbicidal action against various weeds and crops

Connection according to example Dose kg AS / ha ALM SAL LOM ECG wheat sugar beet Soybean alfalfa 1 2.4 0.6 1 4 - 1 3 • 1 2 _4 1 ' 20 2.4 0.6 1 2 2 5 1 1 NJ NJ 5 21 2.4 0.6 1 2 2 3 1 1 1 1 22 2.4 1 1 1 1 _2 .2 I

ALM = Alopecurus myosuroides SAL = Setaria lutescens LOM = Lolium multiflorum ECG = Echinochloa crus galli

Claims (3)

54 241 18 1, herbicidal agent, characterized in that it contains as active ingredient a compound of general formula R ₁
- ο - / VO-CH- (CH ₂ ) -Z v / or in or = Hydrogen or halogen, = Hydrogen, (C, -C,) - alkyl or halogen = hydrogen or (Cj-Cj-alkyl, = an integer from 0 to 2 = a group aer formula 0 0 It ti -C-OR ₉ , -C-SI I » e, O? 6
it c-u-n. * l ^R 8 ' . ca, CH _Q OH _S or -CH ₀ -O-SO ₀ -R ₁ O. 54 241 18 t - $$ = H, _(C.-C12) alkyl, <* ^as optionally 1 to 6 times by halogen and / or hydroxy, (C.-Cg) alkoxy, (Cj-Cj-alkylthio, (C ₁ -CG) -Alkoxy (C ₂ -Cg) -alkoxy, halo-iC.-CgJ-alkoxy, methoxy-ethoxy-ethoxy, (C ₁ -C.) - Alkylamino, di- (C ₁ -C,) - alkylamino-phenyl, oxiranyl or phenoxy substituted, the latter also one to two times by halogen and / or (C ₁ -C,) - Alkyl substituted sän can; (C ₅ -C ₆₎ cycloalkyl, halo (C ₅ -CG) alkyl, (Co-Cg) alkenyl, halo _(C3 -CG) alkenyl, (C ₅ -CG) cycloalkenyl, ( C ₃ -C.) - alkynyl which is optionally mono- or disubstituted by (C ₁ -Cg) -alkyl, phenyl, halogen and / or (C ₁ -C ₂ ) -alkoxy, Phenyl) optionally substituted once to three times by (C ₁ -C 4 alkyl, (C ₁ -C 4 alkoxy, halogen NO ₂ and / or CF-; Furfuryl, tetrahydrofurfuryl or a cation equivalent of an organic or inorganic base; R3 = (C ₁ -Cg) -AlLyI, which is optionally substituted by (Cj-C ^) - alkoxy, halogen or also mono- to trisubstituted by (C ₁ -C.) - Alkyl and / or halogen-substituted phenyl; (Co-Cg) -alkenyl or phenyl which is optionally monosubstituted to trisubstituted by (C ₁ -C 6 -alkyl and / or halogen,
means R and R _{5 are the} same or different and are H, (C ₁ -C ₄ ) -alkyl, hydroxy-iC, -Cg) -alkyl, (C ₅ -Cg) -cycloalkyl or phenyl, which may be mono- to trisubstituted by (C ₁ -C 4) -alkyl, (C ₁ -C 4 -alkoxy, halogen 52 241 18 and / or CFo is substituted, with the proviso, mean or together form a methylene chain having 2, 4 or 5 members in which a CHp group may optionally be replaced by 0, NH or N (CHO), Rg = H or CHo, R, ₇ = H, CHo or C ₂ H ₅ , Rg = H, CHo ₉ C ₂ II ₅ or phenyl, Rq and R ₁ Q are the same or different and are (C ₁ -C.) - Alkoxy, (C .. -C.) - Alky It hi ο, (C ₁ -C.) -Alk lamino or DL- (C ₁ -C.) - Alkylamino or together represent a radical of the formula --NR ₁₂ , R ₁₁ = (C ₁ -C ₆ ) -alkyl, (C ₁ -Cg) 'haloalkyl, C ₃ -C ₅ - or Cg -cycloalkyl, (C ₃ -Cg) -alkenyl, phenyl, (C ₁ -C ₄ ) -Alkylphenyl, (Cj-C.) - Alkoxyphenyl, halophenyl, trifluoromethylphenyl, nitrophenyl or a radical of the formula l · -CH-O represents, as well as R ₁₂ = (C ₁ -C ₄ ) -alkyl, or phenyl which is optionally mono- to trisubstituted by halogen, CF ₂ , NO ₂ and / or (CC,) -alkyl, means, in addition to extenders and / or surface-active agents contain", 2β herbicidal agent characterized in that it contains as active ingredient a compound of formula 1 in the form of its D-enantiomer (based on the atom located between O and) as a chiral center) in addition 52 241 18 Extenders and / or surface-active agents. 3. Herbicidal agents, characterized in that they contain as active compound compounds of the formula I in which R _{2 is} (C ₁ -C ₂ ) -alkyl which is optionally substituted 1 to 6 times by halogen and / or by hydroxy, (C ₁ -C -g) Alkoxy, (C ₁ -C ₁ ) -alkylthio, (O ₁ -Cg) -alkoxy (C ₂ -CG) -bikoxy, halo (C ₁ -C ₄ ) -alkoxy, methoxy-ethoxy-ethoxy, (C ₁ -C.) - Alkylamino, di- (C ₁ -C ^ -alkylamino, phenyl, oxiranyl or phenoxy substituted, the latter also% in to triple 'by halogen and / or (C.-C.) (C ₅ -C 6) -cycloalkyl, halogeno (C 1 -C 9) -cycloalkyl, (C 0 -C ₅ ) -alkenyl, * halogeno (C 1 -C 6) -alkenyl, (C ₅ -) -alkoxy, C 9) -cycloalkenyl, (C ₃ -C ₄ ) -alkynyl, which is optionally mono- or disubstituted by (C ₁ -Cg) -alkyl, phenyl, halogen and / or (C ₁ -C ₂₎ -alkoxy, phenyl which is optionally mono- to disubstituted by (C ₁ -C) -alkyl, (C ₁ -C ₄ ) -alkoxy, halogen, NO ₂ and / or CiV; furfuryl, tetrahydrofurfuryl, or a cation equivalent of an organisdBn or anorg Anischen base, and the remaining radicals have the meanings given in point 1, in addition to extenders and / or surface-active agents. 4 · Herbicidal agents, characterized in that they contain as active ingredient compounds of formula I in the form of its D-enantiomer (based on the between O and (CHP). Located ₀ C-Atorn as a chiral center), in addition to extenders and / or surface-active agents , 54 241 5. Herbicidal agents, characterized in that they as active ingredient a compound of formula OCH-COOCH in addition to extenders and / or surface-active agents. 6 "herbicidal composition, characterized in that it contains as active ingredient a compound of the formula OCH-COOC ₂ Hp CHo in addition to extenders and / or surface-active agents contain » 7. Herbicidal agents, characterized in that they as active ingredient a compound of formula OCH-COOC ₃ H ₇ (η) in addition to .stretching agents and / or surface-active agents 54 241 -16 -43- 8 _β herbicidal agent, characterized in that it contains as active ingredient a compound of formula OGH-COOGoH ₇ Ci) CH ₃ in addition to extenders and / or surface-active agents. 9 »herbicidal composition, characterized in that it contains as active ingredient a compound of the formula ΙΛ- OCH-COOCH f - in addition to extenders and / or surface-active agents. 10, herbicidal compositions, characterized in that they contain as active ingredient a compound of the formula O -T v> _ OCH in addition to extenders and / or surface-active agents. 54 241 18 Herbicidal agent, characterized in that it contains as active ingredient a compound of formula in addition to extenders and / or surface-active agents