DD149007A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions containing new PhenoxycarbonsÄure carbonylalkylestern. The aim of the invention is the provision of agents with improved herbicidal activity, broad spectrum of activity and good tolerability in crops. According to the invention, the new agents contain phenoxycarboxylic acid carbonylalkyl esters of the formula I in which R & exp1 !, R & exp2 !, R & exp3! and R & exp4! independently of one another represent hydrogen or alkyl. Furthermore, for example, R & exp5! Hydroxy, optionally substituted alkoxy, the radical (formula); R & Exp6! Hydrogen, optionally substituted alkyl, alkenyl, alkynyl, optionally substituted aryl; R & exp7! optionally substituted alkyl, optionally substituted aryl, alkenyl, alkynyl and the like; X is hydrogen or chlorine.

Description

Berlin, 6.6.1980

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Herbicidal agent Field of application of the invention

The invention relates to herbicidal compositions containing new Phenoxycarbonsäure carbonyl-alkyl ethers, a process for their preparation and their use ale herbicides,

Characteristic of the known technical solutions

Ee is already known that certain Phenoxycarbonsäureester have herbicidal properties. Thus, for example, methyl 5- (2-chloro-4-trifluoro-methyl-phenoxy) -2-nitro-phenoxy-propionate and 5- (2-chloro-4-trifluoro-ethyl-phenoxy) - 2-nitro- </. Ethyl phenoxy-propionate be used for weed control (see US Patent 4,093 and DE-OS 2,311,638). The effectiveness of these substances is good for both pre-emergence and post-emergence applications. The disadvantage, however, is that some difficult-to-control weeds and grass weeds are not always fully grasped. In addition, the compatibility in some cultures, eg. As cereals, not always fully sufficient.

Object of the invention

The aim of the invention is the provision of agents with improved herbicidal activity, broad spectrum of activity and good plant tolerance in all crop plants.

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Explanation of the essence of the invention

The invention has for its object to find new Phenoxycarboneaure carbonylalkylester, which have the required properties and which are suitable as active ingredient in herbicidal agents »

Ee were now new Phenoxycarbonsäure carbonylalkylester of the formula

R ¹ R ³

0-C-CO-OC-CO-R ⁵ R ⁴

(I)

in which

R, R, R and R independently of one another represent hydrogen or alkyl,

R is hydroxy, or alkoxy, alkylthio, dialkylamino, cyano or halogen optionally substituted alkoxy, alkenoxy, alkynoxy, aralkoxy or aryloxy or the radical

N ₇ stands in which

R is hydrogen, alkyl optionally substituted by alkoxy, alkylthio, dialkylamino or cyano, alkenyl, alkynyl, cycloalkyl, aralkyl, optionally substituted by alkyl, alkoxy, alkylthio,

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Alkoxycarbonyl, halogen, haloalkyl and / or nitro substituted aryl

stands",

R is alkyl optionally substituted by alkoxy, alkylthio, dialkylamino or cyano, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl optionally substituted by alkyl, alkoxy, alkylthio, alkoxycarbonyl, halogen, haloalkyl and / or nitro, or

R and R together with the nitrogen atom to which they are bonded represent an optionally substituted, optionally fully or partially unsaturated and / or optionally benzo-halogenated mono- or bicyclic having up to 15 carbon atoms, which may optionally contain 1 to 3 further nitrogen atoms or another Contains oxygen or sulfur atom as heteroatoms,

and

X is hydrogen or chlorine,

found.

It has furthermore been found that phenoxycarbonylcarbonylalkyl esters of the formula (I) are obtained when phenoxycarboxylic acid chlorides of the formula

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in which

R, R and X are as defined above,

with <? C- hydroxy-carboxylic acid derivatives of the formula

R ³

¹ ς

HO-C- (X) -R ⁰ (III)

in which

3 4 5

R, R and R have the abovementioned meaning,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

Finally, it has been found that the new Phenoxycarboneäure carbonylalkylester of formula (I) have strong herbicidal properties.

Surprisingly, the phenoxycarbonyl-carbonylalkyl esters according to the invention have a significantly better herbicidal action than the compounds known from the prior art, methyl 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-64-phenoxy-propionate and 2-chloro-4-trifluoromethyl-phenoxy) -2-nitroof. phenoxy-propionic acid ethyl ester, which are the chemically closest substances of the same direction of action. It is particularly advantageous that the substances according to the invention, especially when used according to the pre-emergence method, are better for destroying weeds and grass weeds, which are difficult to control.

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such as Galium and Cyperus, are suitable as the aforementioned known substances. In addition, the active compounds according to the invention are distinguished in a post-emergence application by a better compatibility with cereals than the abovementioned previously known substances.

The phenoxycarbonyl-carbonylalkyl esters according to the invention are generally defined by the formula (I). In this formula, R, κ, R and R independently of one another preferably represent hydrogen or methyl, R preferably denotes hydroxyl, where appropriate by C ₁ -C ₄ -alkoxy, C ₁ -C -alkylthio, Di-C -C. alkylamino, cyano or chlorine-substituted C.-C alkoxy, C ₃ -C _Q -alkenoxy, C ₃ -C ₆ alkynoxy, benzyloxy or phenoxy or the radical

N ^, wherein R is preferably hydrogen, optionally substituted by

C -C -alkylthio, di-C 1 -C 4 -alkylamino or cyano-substituted C -C -alkyl, C 1 -C 8 -alkenyl, C -C -alkynyl, C 1 -C 6 -cycloalkyl, benzyl, phenylethyl or for substituted phenyl optionally substituted by C -C ₄ alkyl, ^c i ^"C 4" alkoxy, C ^ C ^ alkylthio, C.-C alkoxy-carbonyl, fluorine, chlorine, bromine, trifluoromethyl or nitro,

R is preferably optionally substituted by CC ₄ -alkoxy, C ^ -C ^ alkylthio, di-C -C ₄ alkylamino or cyano-substituted C ₁ -C ₄ -alkyl, C, -CG-alkenyl, C ₃ -C ₆ - Alkynyl, Cj-Cg-cycloalkyl, benzyl, phenylethyl or optionally substituted by C -C ₄ alkyl, CC ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C -C ₄ -alkoxy-carbonyl. Fluorine, chlorine,

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Bromine, trifluoromethyl or nitro substituted phenyl, or

R and R together with the nitrogen atom to which they are attached are preferably each pyrrolidyl or morpholinyl optionally substituted by 1 or 2 methyl or ethyl groups, piperidyl optionally substituted by 1 to 3 methyl or ethyl groups, indolyl, tetrahydroindolyl, perhydroindolyl , Tetrahydroquinolyl, tetrahydroisoquinolyl, perhydroquinolyl, perhydrohequinolyl, perhydrothiazolyl or perhydroazepinyl. X is preferably hydrogen or chlorine.

If 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro- xrC- phenoxy-propionic acid chloride and methyl hydroxyacetate are used as starting materials, the course of the process according to the invention can be represented by the following formula scheme:

CH.

-HCl

+ HO-CH ₂ -CO-OCH ₃

CH ₃

0-CH-CO-O-CH ₂ -CO-OCH

The Phenoxycarbonsäurechloride required as starting materials in carrying out the process according to the invention

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are generally defined by the formula (II). In this

R 1 and R 2 preferably represent those radicals which are already mentioned in connection with the description of the compounds of formula (I) according to the invention preferably for these radicals.

Examples of the phenoxycarboxylic acid chlorides of the formula (II) which may be mentioned are:

5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nifro- ^ -phenoxy- and 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro- t- phenoxy-propionic acid chloride ,

The phenoxycarboxylic acid chlorides of the formula (II) are known or can be prepared by customary methods (cf US Pat. No. 4,093,446). The hitherto unknown phenoxycarboxylic acid chlorides can be synthesized by reacting phenoxycarboxylic acids of the formula

CO-OH

(IV)

in which

12 R, R and X are as defined above «

with chlorinating agents such. As thionyl chloride, optionally using diluents such as. B. benzene or ethylene chloride, reacted at temperatures between 10 and 100 ⁰ C and removed by distillation readily volatile components after the end of the reaction.

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The phenoxycarboxylic acids of the formula (IV) are likewise known or can be prepared by customary processes (compare U8-PS 4 093 446). The compounds of the formula (IV) are thus obtained by reacting phenoxycarboxylic acid esters of the formula

(V)

in which

1 2

R, R and X are as defined above

R is alkyl (in particular methyl or ethyl), with aqueous Alkalihydroxidlaugen, preferably with sodium hydroxide or potassium hydroxide, which optionally with organic solvents such. As methanol, ethanol or dioxane are diluted, reacted at temperatures between 20 and 100 ⁰ C.

As examples of the phenoxycarboxylic acids of the formula (V)

be named:

5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-ε-phenoxy- and 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro- «Λ -

phenoxy-propionic acid.

The phenoxycarboxylic esters of the formula (V) are also known or can be prepared by customary processes (cf.

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U.S. Pat. No. 4,093,446) to obtain the compounds of formula (V) by reacting phenol derivatives of the formula

(VI)

in which

X has the meaning given above,

or their sodium or potassium salts,

with oC-halo-carboxylic acid esters of the formula

Hal-C-CO-OR (VII)

'#

in which

12

R and R are as defined above, R is alkyl (especially methyl or ethyl)

stands and Hai stands for chlorine or bromine,

optionally in the presence of an acid binder such as. For example, sodium methylate or potassium carbonate and optionally using a polar diluent such as. As methanol, acetonitrile or sulfo, at temperatures between 20 and 100 ⁰ C ·

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As examples of the Phenoxycarbonsäureester of formula (V) may be mentioned:

5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro- << phenoxy and 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-aC phenoxy-propionic acid methyl ester, and - ethyl ester.

The phenol derivatives of the formula (VI) are known (see US Pat. No. 4,093,446). As examples of the phenol derivatives of the formula (VI) may be mentioned: 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenol and 5- (2,6-dichloro-4-trifluoromethyl-phenoxy ) -2-nitro-phenol.

The £-halogenated carboxylic acid esters of the formula (VII) are also known. Examples of these are: * £ chloro-propionic acid methyl ester and ethyl and el-bromo-propionsäuremethyleeter and ethyl acetate.

The oC-hydroxycarboxylic acid derivatives furthermore required as starting materials for carrying out the process according to the invention are generally defined by the formula (III). In this formula, R _t R and R preferably represent those radicals which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The <> E-hydroxycarboxylic acid derivatives of the formula (III) are known or can be prepared by customary processes (cf DE-OS 2 201 432).

The not yet known o ^ -hydroxy-carboxylic acid of the formula

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R ³ R ⁶ / HO-C-CO-N R *

(III a)

in which

R _e R, R and R have the abovementioned meaning,

obtained, for example, by oC-halo -carbon acid amides of the formula

R ³ R ⁶

Hal-C-CO-N '(VIII)

in which R ³ , R ⁴ , R ⁶ Hal represents chlorine or bromine.

R, R, R and R have the abovementioned meaning and

in a first stage with excess sodium or potassium acetate, optionally in the presence of a catalyst such as. As tetrabutylammonium bromide and optionally using a diluent such as. As acetic acid or toluene, at temperatures between 20 and 200 ⁰ C and in a second stage, the resulting Acetoxycarbonsäureamide the formula

R ³ R ⁶

CH ₃ -CO-OC-CO-N > (IX)

R ⁴ R ⁷

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in which

R, R, R and R have the abovementioned meaning, deacylated by reaction with dilute aqueous-alcoholic sodium hydroxide at temperatures between 20 and 150 ⁰ C.

As examples of the c /. Hydroxycarboxylic acid derivatives of the formula (III) may be mentioned:

Hydroxyacetic acid, oi. Hydroxypropionic acid and oi-hydroxyisobutyric acid methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, benzyl ester, -phenyl ester, -methylamide, -ethylamido-n-propylamide, -iso-propylamide, -n-butylamide, -iso-butylamide, -dimethylamide _t -diethylamide, -di-n-propylamide, -di-iso-propylamide, -N-methyl-N-isopropylamide, -N-methyl-N-i8o-butylamide, -N-methyl-N-sec, -butylamide, -di- (2-ethylhexyl) -amide, -N-methyl-N- (2-cyanoethyl-amide, -di- (2-methoxy-ethyl-amide, -diallylamide, -N-methyl-N-propargylamide, -N-methyl-N- (1-methyl-propargyl) -amide, -dipropargylamide , -cyclopentylamide, -N-methyl-N-cyclopentylamide, -cyclohexylamide, -N-methyl-Nc-clohexylamide, -anilide, -2-nitro, 3-nitro and -4-nitro-phenylamide, -2- Chloro, -3-chloro and 4-chlorophenylamide, 2,4-dichloro, 2,5-dichloro, -3,4-dichloro, and -SS-dichloro-phenylamide, -2-methyl , 3-methyl and 4-methyl-phenylamide, -N-methylanilide, -N-methyl-N- (2-methyl-phenyl) -amide, -N- methyl-N- (2-nitrophenyl) - _# -N-methyl-N- (3-nitrophenyl) -, -N-methyl-N- (4-nitrophenyl) -amide, -N-methyl-N- (2-methyl) chlorophenyl) -, -N-methyl-N-isis-chlorophenyl) -, - N -methyl-N- (4-chlorophenyl) -amide, -N-methyl-N- (3-nitro-6-methyl-phenyl) -amide, -N-ethylanilide, -N-ethyl-N- (2-nitro-phenyl) -, -N-ethyl-N- (3-nitrophenyl) -, -N-ethyl-N- (4-nitro-phenyl) phenyl) -amide, -N-ethyl-N- (2-chlorophenyl) -, -N-ethyl-N-isopropylchloro-phenyl) -, -N-ethyl-

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N- (4-chlorophenyl) -araid _f -N-ethyl-N- (3-nitro-6-methylphenyl) -amide, -N-propyl-anilide, -N-propyl-N- (2-nitrophenyl. ), -N-propyl-N- (3-nitro-phenyl) -, -N-propyl-N- (4-nitro-phenyl) -amide, -N-propyl-N- (2-chloro-phenyl) , -N-propyl-N-isopropylchloro-phenyl), -N-propyl-N- (4-chloro-phenyl) -amide, -N-propyl-N- (2-methylphenyl) -, -N-propyl-N- (3-methylphenyl) -, -N-propyl-N- (4-methyl-phenyl) -amide _# -M-propyl-N- (3-nitro-6-methylphenyl) - amide, -N-butyl-anilide, -N-butyl-N- (2-nitro-phenyl) -, -N-butyl-N- (3-n-tro-phenyl) -, -N-butyl-N- (4-nitro-phenyl) -amide _# -N-butyl-N- (2-chlorophenyl) -, -N-butyl-N- (3-chlorophenyl), -N-butyl-N- (4- chlorophenyl) amide, -N-butyl-N- (2-methyl-phenyl) -, -N-butyl-N- (3-methyl-phenyl) -, -N-butyl-N- (4-methyl-phenyl ) -araid, -N-butyl-N- (3-nitro-6-roethyl-phenyl) -amide, -N-isobutylanilide, -N-iso-butyl-N- (2-nitro-phenyl) -, -N -iso-butyl-N- (3-nitro-phenyl) - _# -N-iso-butyl-N- (4-nitro-phenyl) -amide, -N-i8o-butyl-N- (2-chloro) phenyl), -N-iso-butyl-N- (3-chlorophenyl) -, -N-i3o-butyl-N- (4-chlorophenyl l) -amide _f -N-isobutyl-N- (2-methylphenyl) -, -N-isobutyl-N- (3-hydroxyethyl) -phenyl, -N-i80-butyl-N- 4-methyl-phenyl) -9iuide, -N-iso-butyl-N- (3-nitro-6-methylphenyl) -amide, -naphth (l) ylaraid, -naphth (2) ylamide, -N-methyl -N-naphth- (I) ylamide, -N-methyl-N-naphth (2) ylamide, -N-ethyl-N-naphth (1) ylamide, -N-ethyl-N-naphth (2) ylamide, Nn-propyl-N-naphth (2) ylamide, N-iso-propyl-N-naphth (2) ylamide, -Nn-butyl-N-naphth (2) ylamide, N-isobutyl-N-naphthene (2 ) ylamide, benzylamide, dibenzylamide, N-methyl-N-butylamide, N-ethyl-N-benzylamide, N-propyl-N-benzylamide, N-butyl-N-benzylamide, pyrrolidide, -2 -methylpyrrolidide, -raorpholid, -piperidide, r2-methyl-piperidide, -4-methyl-piperidide, -2,4-dimethyl-piperidide, -2,4,6-trimethyl-piperidide, -2-ethyl-piperidide, - 4-ethyl-piperidide, 2,4-diethyl-piperidide, -2,4,6-triethyi-piperidide, 2-methyl

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4-ethyl-piperidide, ^ -ethyl ^ -methyl-piperidide, 2-methyl-5-ethyl-piperidide, ^ -ethyl-S-methyl-piperidide, -2-methyl-6-ethyl-piperidide, -1,2 , 3,4-tetrahydroindolide, 2-methyl-1,2,3,4-tetrahydroindolide, -perhydroindolide, 2-methylperhydroindolide, -2,2-dimethylperhydroindolide, -1,2,3,4-tetrahydroquinolone, ~ 2-methyl-l, 2,3,4-tetrahydroquinolide, -perhydroquinolide, -2-methyl-perhydroquinolide, -4-methylperhydroquinolide, -1,2,3,4-tetrahydroiso-quinolide and perhydroisoquinoline.

The *> C- halocarboxamides of the formula (VIII) are known or can be prepared analogously to known processes. You get it z. ß. by reacting o ^ -Halogencarbonsäurehalogeniden, such as. For example, chloroacetyl chloride with ammonia or primary or secondary amines, optionally in the presence of an acid acceptor such. Potassium hydroxide (compare 0. Agric. Food Chem. 4 (1956), 518-522).

Examples of the halocarboxamides of the formula (VIII) are:

Chloroacetic, chororopropionic and c1-chloroisobutyric acid methyl amide, ethyl amide, n-propyl amide, di-propyl amide, n-butyl amide, iso-butyl amide, dimethyl amide, diethyl amide, di -n-propylamide, -di-isopropylamide, -N-methyl-N-isopropylamide, -N-methyl-N-iao-butylamide, -N-methyl-N-sec-butylamide, -di- ( 2-ethyl-hexyl) -amide, -N-methyl-N- (2-cyano-ethyl-amide, -di- (2-methoxy-ethyl) -amide, -diallylamide, -N-methyl-N-propargyl- amide, N-methyl-N- (1-methyl-propargyl) -amide, -dipropargyl-amide, -cyclopentylamide, -N-methyl-N-cyclopentyl-amide, -cyclohexyl-amide, -N-methyl-N- cyclohexylamide-anilide, -2-nitro, -3-nitro and -4-nitro-phenylamide, 2-chloro and 3-chloro and 4-chloro

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phonylamide, 2,4-dichloro, 2,5-dichloro, 3,4-dichloro and 3,5-dichloro-phenylamide, 2-methyl, 3-methyl and 4-dicarboxylic acid. methylphenylamide, -N-methylanilide, -N-methyl-N- (2-methyl-phenyl) -amide, -N-methyl-N- (2-nitro-phenyl) -, -N-methyl-N- ( 3-nitrophenyl), -N-methyl-N- (4-nitro-phenyl) -amide, -N-methyl-N- (2-chlorophenyl) -, -N-methyl-N-iso-chloro phenyl), -N-methyl-N- (4-chloro-phenyl) -amide, -N-methyl-N- (3-nitro-6-hydroxyethyl) -amide, -N-ethyl-anilide, -N-ethyl -N- (2-nitro-phenyl) _-t -N-ethyl-N- (3-nitro-phenyl) - _# -N-ethyl-N- (4-nitro-phenyl) -amide _t -N-ethyl- N- (2-chloro-phenyl) -, -N-ethyl-N-CS-chlorophenyl) -, -N-ethyl-N- (4-chloro-phenyl) -araid, -N-ethyl-N- (3 -nitro-6-methyl-p-benzyl) -amide, -N-propyl-anilide, -N-propyl-N- (2-nitro-phenyl) -, -N-propyl-N- (3-nitro-phonyl) - , -N-propyl-N- (4-nitro-phenyl) -amide _# -N-propyl-N- (2-chlorophenyl) -, -N-propyl-N-isopropylchloro-phenyl) -, - N-propyl-N- (4-chlorophenyl) -8mid, -N-propyl-N- (2-methylphenyl) -, -N-propyl-N- (3-methylphenyl) -, -N-propyl -N- (4-hydroxyphenyl) -araid, -N-pcopyl-N- (3-nitro-6-methyl-phenyl) -amide, -N-butyl-anilide, -N-butyl-N- (2-nitro-phenyl) -, -N-butyl-N- (3-nitro-phenyl ) -, -N-butyl-N- (4-nitro-phenyl) -amide, N-butyl-N- (2-chloro-phenyl) - _f N-butyl-N- (3-chloro-phenyl) , N-butyl-N- (4-chloro-phenyl) -amide, -N-butyl-N- (2-methylphenyl) -, -N-butyl-N- (3-methylphenyl) -, - N-butyl-N- (4-methyl-phenyl) -araid, -N-butyl-N- (3-nitro-6-methylphenyl) -amide, -N-hexybutyl-anilide, -N-hexybutyl-N - (2-nitro-phenyl) -, -N-iso-butyl-N- (3-nitro-phenyl) -, -N-18-butyl-N- (4-nitro-phenyl) -amide, -N- isobutyl-N- (2-chloro-phenyl) -, -N-isobutyl-N- (3-chloro-phenyl) - _f N-isobutyl-N- (4-chloro-phenyl) -amide, -N-iso-butyl-N- (2-methylphenyl) -, -N-iso-butyl-N- (3-ethyl-phenyl) -, -N-iso-butyl-N- (4-methyl-phenyl) -amide, -N-i8o-butyl-N- (3-nitro-6-raethylphenyl) -amide, -naphth (l) ylaraid _f -naphth (2) ylamide _f -N-methyl-N-naphth (l) ylamide _t -N _r inethyl-N-naphthyl (2) ylaraid, -N-ethyl-N-

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naphthyl (1) ylamide, N-ethyl-N-naphth (2) ylamide, N-propyl-N-naphth (2) ylamide, N-isopropyl-N-naphth (2) ylamide, -N- n-butyl-N-naphthyl (2) ylamide, N-iso-butyl-N-naphth (2) -ylamide, benzylamide, dibenzylamide, N-methyl-N-benzylamide, N-8-thyl-N-benzylamide, -N-propyl-N-benzylamide, -N-butyl-N-benzylamide, -pyrrolidide, -2-methyl-pyrrolidide, -morpholide, -piperidide, -2-methyl-piperidide, -4-methyl-piperidide, -2 , 4-dimethyl-piperidide, -2,4,6-trimethyl-piperidide, -2-ethyl-piperidide _t -4-ethyl-piperidide, 2,4-diethyl-piperidide, -2,4,6-triethyl- piperidide, 2-methyl-4-ethyl-piperidide, 1-ethyl-1-methyl-piperidide, 2-methyl-5-ethyl-piperidide, 2-ethyl-5-methyl-piperidide, 2-methyl-6 -θthyl-piperidide, -1,2,3,4-tetrahydroindolide, 2-methyl-l, 2,3,4-tetrahydroindolide, -perhydroindolide, 2-methyl-porhydroindolide, -2,2-dimethyl-perhydroindolide, 1,2,3,4-tetrahydroquinolide, 2-methyl-1,2,3,4-tetrahydroquinolide, -perhydroquinolide, 2-methyl-perhydroquinolide, 4-methyl-perhydroquinolide, -1,2,3, 4-tetrahydroisoquinolide un d -perhydroisoquinolide.

The process according to the invention is preferably carried out using suitable solvents or diluents. As such, virtually all inert organic solvents come into question.

These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as gasoline, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene. Ethers, such as diethyl and dibutyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methylethyl, methyl isopropyl and methyl isobutyl ketone, nitriles, such as acetonitrile and propionitrile, and aprotic polar solvents.

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medium, like ζ. Β. Dimethylformamide, dimethyl sulfoxide, sulfolane and hexamethylphosphoric triamide.

All acid acceptors can use all customary acid binders. Alkali metal carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylarain and pyridine, have proven particularly useful.

The reaction temperature can be varied within a wider range. In general, one works between -20 and 100 ⁰ C, preferably between 0 and 50 ⁰ C.

The process of the invention is generally carried out at atmospheric pressure.

For carrying out the process according to the invention, 1 to 1.5 mol, preferably 1 to 1.2 mol, of ai -hydroxycarboxylic acid derivative of the formula (III) and 1 to 5 mol of acid binder are employed per mole of phenoxycarbonyl chloride of the formula (II). The reaction is generally carried out in a suitable diluent, and the reaction mixture is stirred for several hours at the required temperature. Thereafter, an organic solvent, for. As toluene, and the organic phase is working as usual by washing, drying and distilling off the solvent.

Some of the new compounds are in the form of oils, some of which can not be distilled without decomposition.

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however, by so-called "annealing", d. H. can be freed from the last volatile fractions by prolonged heating under reduced pressure to moderately elevated temperatures and purified in this way. The refractive index serves for their characterization.

As far as the products are obtained in solid form, they can be purified by recrystallization. The melting point is used for characterization.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, anti-sprouting agents and in particular as weedkillers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds according to the invention can, for. B. be used in the following plants;

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, iiatricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,

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Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.

Monocotyledonous Weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleccharis, Scirpus, Paspalum, Ishaemum , Sphenoclea, Oactyloctenium, Ag rust, Alopecuruö, Apera. · -.

Monocotyledonous cultures of the genera: Oryza, Zea, -Triticum, Hordeujn, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

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

The compounds are suitable depending on the concentration for total weed control, z. B. on industrial and railway tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, z. As forestry, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops become.

The active compounds according to the invention show a very good action against weeds and weed grasses. They are particularly useful for the elimination of difficult-to-control weeds and grass weeds such as Galium and Cyperus.

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To further improve the spectrum of action, combinations with other herbicides are possible, especially with N-benzthiazol-2-yl-N, N'-dimethyl-urea.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, active substance-impregnated natural and synthetic substances and microencapsulations in polymeric substances.

These formulations are prepared in a known manner, for. B. by mixing the active compounds with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents "In the case of the use of V / asser as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. For example, petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and Dimethyleulfoxid, and water.

Suitable solid carriers are:

z. Natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates; as a solid carrier

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AP C 07 C / 219 2 19063 - 21 - 56 89Ρ / 11

for granules there are suitable: _# example crushed and fractionated natural rocks such as calcite, marble, pumice ,, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, Kokoenußschalen, corn cobs and tobacco stalks ; as Eraulgier- and / or foaming agent in question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ether, 2. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: 2. B. Lignin-sulphite liquors and methylcellulose.

Ee may be used in the formulations adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

There may be dyes, such as inorganic pigments, for. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, Azol-Metallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90 %.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds in admixture with known herbicides, ready-to-use formulation or tank mixing being possible. Also one

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Mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, bird repellents, growth factors, plant nutrients and soil conditioners, is possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, for. B. by pouring, spraying, spraying, spreading.

The active compounds according to the invention can be applied both before and after emergence of the plants. The application is preferably carried out before emergence of the plants, ie in the pre-emergence method. They can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary within larger ranges. It depends essentially on the type of effect desired. In general, the application rates are between 0.05 and 10 kg of active ingredient per ha, preferably between 0.1 and 5 kg / ha.

embodiment

The invention is explained in more detail below with reference to some examples.

The good herbicidal activity of the compounds according to the invention is evident from the examples below.

219063

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In these examples, the following substances are used as reference substances:

0-CH-COOC ₂ H

egg

^CH 3

0-CH-COOCH.

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Example A Pre-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient. It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in % damage in comparison to the development of the untreated control. It means:

O % s no effect (as untreated control) 100 % = total destruction

In this test, the compound of the invention described in Example (14) shows a significantly better activity against Cyperus than the known comparison substance (A).

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Example B

 Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient. It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in % damage in comparison to the development of the untreated control. It means:

0 % «no effect (as untreated control) 100 % a total annihilation

In this test, the compounds according to the invention described in Examples (2) and (13) show a significantly better action against galium than the known comparative substance (B).

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Example C Post-Renewal Test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

With the preparation of active compound is injected test plants, which have a height of 5 to 15 cm, so that the particular desired amount of active ingredient per unit area is applied. The concentration of the spray mixture is chosen so that in 2000 1 water / ha, the respective desired amount of active ingredient is applied. After three weeks, the degree of damage of the plants is rated in % damage in comparison to the development of the untreated control. It means:

0 % = no effect (as untreated control) 100 % = total destruction

In this test, the compound according to the invention described in Example (14), with equally good action against Stellaria and Matricaria, shows a significantly better tolerability in wheat than the known comparison substance (A).

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4 Q Λ t O '^ ^C ° ^{7 c / 219} ° ⁶³

19063 -27- 56 890/11

Example D. ,.

Defoliation and drying of leaves in cotton

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and filled with water to the desired concentration.

Cotton plants are grown in the greenhouse until fully unfolding the fifth leaf. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After one week the leaf fall and the drying out of the leaves are scored compared to the control plants. It means:

0 no drying of the leaves, no leaf fall + slight drying out of the leaves, less

Leaf fall, ♦ + severe dehydration of leaves, heavy leaf fall,

♦♦ + very strong drying of the leaves, very strong leaf fall.

In this test, the compounds described in Examples (5), (12) and (14) show very good activity.

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Example E Growth inhibition at Baumtvolle

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the specified amounts of solvent and emulsifier and filled with water to the desired concentration.

Cotton plants are grown in the greenhouse until fully unfolded on the fifth foliage sheet. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks, the growth of the plants is measured and the growth inhibition calculated as a percentage of the growth of the control plants. 100 % growth inhibition means the stoppage of growth and 0 % growth corresponding to that of the control plants.

In this test, the compound described in Example (12) shows a very strong antiproliferative activity.

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Herstellunqsbeispiele

 rr O-CH-CO-O-CH 2 -CO-N - //

CH ₃

A solution of 12.5 g (27 mmol) of 5 ~ (2,6-dichloro-4-trifluoro-ethyl-phenoxy) -2-nltro- </. -phenoxy-propionic acid chloride in 30 ml of toluene is added dropwise to a cooled to ⁰ to 5 ⁰ C solution of * 5 g (30 mmol) of hydroxy-oleic acid-N-methyl-anilide and 10 ml of pyridine in 70 ml of toluene. The reaction mixture is stirred overnight at room temperature, diluted with 300 ml of toluene, washed neutral, dried, filtered and concentrated. This gives 13 g (81 % of theory) of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro- pC- phenoxy-propoxonic acid-1-methyl-N-phonyl-carbamoyl-ethyl) ester in the form of a yellowish refractive index oil

n ° ⁴ : 1.5607.

Analogously to Example 1, the compounds of the formula (I) listed in Table 1 below are prepared:

table 1 CF ₃ - Cl G f f O-CxCO-O- ' R (βCO-R ⁵ X > _N0 ₂

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At-melting

play 12 3 4 5 ^point ( ^C ) '"

No. XR ¹ RRRR ^D refractive index

2HH CH ₃ HH -OC ₄ H ₉ -η η ^ ⁴ : 1.5227

O 24 n ": 1.5606

-3

4HHH HH -OC ₂ H ₅ 88

5HH CH ₃ HH -N (CH ₃ J ₂ n ^ ⁴ : 1.5235

6 HH HH CH ₃ -N (CH ₂ -CH = CH _{2) 2} n ^ ^4: 1.5124

7HH CH ₃ HH -Up} n ^ ⁴ : 1.5132

8HHCHHH-NH / n ^: 1.5215

9HH CH ₃ HH -nJV CH ₃ n ^ ⁴ : 1.5312

10 HH CH_H CH, -N - ^> n ^ ⁴ : 1.5760

3 3 _6h WD

11HH CH ₃ H CH ₃ -OC ₂ H ₅ n ^ ¹ : 1.5221

12 Cl H CH ₃ HH -OC ₄ H ₉ -η n ^ ⁴ : 1.5606

13HH CH ₃ HH -OC ₂ H ₅ n ^ ⁴ : 1.5297

14 Cl H CH ₃ HH -OC ₂ H ₅ n ^ ⁴ : 1.5330

15 Cl H CH_H CH, -0 C _o H _c 74

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At-melting

play _± 2 3 4 5 ^point ( ^C);

No. XR ¹ RRRR refractive index

16 Cl H CH ₃ HH -N (CH _£ - ^) ₂

17 Cl H CH ₃ HH -NH- ^ n 60

18 Cl H CH, H H -NH- ^ A-Cl 46

19 Cl H CH, H CH_ -N-AvS 132

20 Cl H CH ₃ CH ₃ CH ₃ -OC ₂ H ₅ njp: 1.5319

21 Cl H CH ₃ HH -OCH ₃ * $ "* '- 1.542

The phenoxycarboxylic acid chlorides to be used as starting materials can be prepared, for example, as follows

Example II-1 CH ₃

Cl is O-CH-CO-Cl

O- ^ V NO ₂ Cl

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9.7 g (82 mmol) of thionyl chloride are added dropwise at room temperature to a solution of 30 g (68 mmol) of 5- (2,6-bichloro-4-trifluoromethyl-phenoxy) -2-nitro- oC- phenoxypropionic acid and 0.5 ml of dimethylformamide in 100 ml of 1,2-dichloroethane. The mixture is refluxed for 4 hours. Charcoal is added, filtered and evaporated. After digesting the oily residue with 100 ml of ligroin, 26.2 g (84 % of theory) of 5- (2,6-dichloro-4-trifluoro-methyl-phenoxy) -2-nitro- oC- phenoxy-propionic acid chloride in the form yellow crystals of melting point 92 ⁰ C.

The phenoxycarboxylic acids required as precursors can be prepared, for example, as follows:

Example IV-I

^{1 r} -.

0-CH-CO-OH

135 g (0.3 mol) of methyl 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitrool-phenoxy-propionate and 30 ml of concentrated sodium hydroxide solution are dissolved in 400 ml of acetonitrile and 150 ml of water for 24 hours stirred at 20 ° C. The solution is concentrated, the residue taken up in 500 ml of water and acidified with 50 ml of concentrated hydrochloric acid. This gives 93 g (71 % of theory) of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro- aL- phenoxy-propionic acid in the form of pale yellow crystals with the melting point of 146 ⁰ C (after recrystallization from toluene / cyclohexane).

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The phenoxycarboxylic acid esters required for the ale precursors can be prepared as follows:

Example V-I

CH ₃ O-CH-CO-OCH-

40 g (0.24 mol) c ^ bromo-propionate are added dropwise to a heated to 50 ⁰ C mixture of 73.6 g (0.2 mole) of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) 2-nitro-phenol, 32 g of potassium carbonate and 200 ml of acetonitrile. The reaction mixture is heated under reflux for 5 hours then poured into 1 1 of water and extracted with 1 1 of toluene. The toluene phase is washed with 300 ml of aqueous sodium hydroxide solution and then with 500 ml of water. After distilling off the solvent in vacuo is obtained as an oil which crystallized upon addition of methanol, 74 g (81 % of theory) of 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro- oi -phenoxy-propionate with the melting point 78 ⁰ C.

Claims (5)

6.6.1980 / AP C 07 C / 219 0.6 3 - 34 - 56 890/11 Claim for invention 1. A herbicidal composition, characterized by a content of at least one Phenoxycarbonsäure carbonylalkylester of the formula R ¹ R ³ Cl 0-C-CO-OC-CO-R ⁵ [2 JU (I) in which R , R, R and R are independently hydrogen or alkyl, R is hydroxy, or alkoxy, alkylthio, dialkylamino, cyano or halogen optionally substituted alkoxy, alkenoxy, alkynoxy, aralkoxy or aryloxy or the radical N stands in which R is hydrogen, optionally substituted by alkoxy, alkylthio, dialkylamino or cyano alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, optionally substituted by alkyl, alkoxy ^ alkylthio, alkoxycarbonyl, halogen, haloalkyl and / or nitro substituted aryl stands. 06/06/1980 _Λ .: * AP C 07 C / 219 063 219063 -35- 56 890/11 R is alkyl optionally substituted by alkoxy, alkylthio, dialkylamino or cyano, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl optionally substituted by alkyl, alkoxy, alkylthio, alkoxycarbonyl, halogen, haloalkyl and / or nitro goes, or R and R together with the nitrogen atom to which they are attached are an optionally sub-.etitierten, optionally fully or partially unsaturated and / or optionally benzannellierten mono- or bicyclic having up to 15 carbon atoms, which optionally 1 to 3 further nitrogen atoms or contains another oxygen or sulfur atom as heteroatom (s), » and X represents hydrogen or chlorine in addition to extenders and / or surfactants. 2. A method for controlling weeds, characterized in that phenoxycarboxylic acid carbonylalkylester of formula (I) is allowed to act on weeds or their Lebensraura. 3 ^ Use of Phenoxycarbonsäure carbonylalkylestern of formula (I), characterized in that they are used for controlling weeds. 06/06/1980 * AP C 07 C / 219 -36 "56 890/11 4. A process for the preparation of herbicidal agents, characterized by mixing Phenoxycarbonsäurecarbonylalkylester of formula (I) with extenders and / or surface-active substances. 5. Use of Phenoxycarbonsäure carbonylalkylestern of formula (I), characterized in that they are used as defoliants and Desiccants.