FR2482589A1 - SUBSTITUTED DIPHENYL ETHERS AND THEIR APPLICATION AS HERBICIDES - Google Patents

Abstract

SUBSTITUTE DIPHENYL ETHERS. THEY RESPOND TO THE FORMULA: (CF DRAWING IN BOPI) IN WHICH A IS OXYGEN OR SULFUR; X IS HYDROGEN OR A HALOGEN; Y IS A HALOGEN OR TRIFLUOROMETHYL; Z IS A HALOGEN OR A NITRO OR CYANO GROUP; R IS HYDROGEN OR AN ALKYL GROUP WITH 1 TO 4 CARBON ATOMS; R IS AN ALKYLIDENE GROUP OR A MONO-SUBSTITUTE ALKYLIDENE GROUP CONTAINING UP TO 3 CARBON ATOMS, IN WHICH THE SUBSTITUTE IS AN ALKYL GROUP HAVING UP TO 4 CARBON ATOMS AND R IS ALKYDROGUS CONTENT, JUST ONE ALKYDROGUS GROUP, 'HAS 10 CARBON ATOMS, OR A CYCLOALKYL GROUP WITH 3 TO 8 CARBON ATOMS, OR AN AGRONOMICALLY ACCEPTABLE IONIC SPECIES. APPLICATION AS A HERBICIDE.

Description

The present invention relates to certain substituted diphenyl ethers

  endowed with herbicidal activity, their preparation and their application to weed control. The invention relates more particularly to substituted diphenyl ethers represented by the formula

0 R 0

  wherein A is oxygen or sulfur; X is from

  hydrogen or halogen; Y is a halogen or trifluoro-

  methyl; Z is a halogen, or a nitro or cyano group; R is hydrogen or an alkyl group containing 1 to 4 atoms

  of carbon; R1 is an alkylidene group or an alkyl group

  mono-substituted dinene containing 1 to 3 carbon atoms, in

  wherein the substituent is an alkyl group containing from 1 to 4 carbon atoms

  carbon mon; and R2 is hydrogen, an alkyl group

  comprising from 1 to 10 carbon atoms, a cyclic group

  alkyl containing 3 to 8 carbon atoms, or an

than agronomically acceptable.

  Examples of halogens represented by X, Y and Z in the formula above are, for example, bromine, chlorine or fluorine, preferably bromine or chlorine. Alkyl groups represented by R 1 and R 2 are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, butyl-test, n-amyl, hexyl and octyl; isooctyl, nonyl, decyl and the like. Examples of alkylidene radicals represented by R 1 are, for example, methylidene, ethylidene or propylidene radicals. Suitable alkoxy or cycloalkyl groups represented by R 2 are methoxy, ethoxy, butoxy, octoxy, as well as cyclopentyl, cyclohexyl, cycloheptyl and

  Similar. As examples of agronomic ionic species,

  R2, alkali metals such as sodium, potassium or lithium, alkaline earth metals such as barium or calcium,

  ammonium, an alkylammonium or an alkanolammonium

  mant 1 to 4 carbon atoms. It is believed that compounds of the formula

  above have a herbicidal activity, according to the pre-

  this invention. Specific examples of compounds within the scope of said formula and preferred in accordance with

  the invention are N - / - 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzene

  ethyl zoylglycinate; N-f-5- (2 ', 4'-dichlorophenoxy) -2

  ispopropyl-nitrobenzoylglycinate; N-sec-butyl-N-

  Ethyl 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate; N - 5 (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycine; ethyl N - / - 2 ', 4'dichlorophenoxy) -2-nitrobenzoyl7alaninate; N - / - 5- (2 ', 4'-dichlorophenoxy) -2-ritrobenzoylglycinate

  methyl; N- [2'-chloro-4-trifluoromethylphenoxy] -2-nitro-

  benzoylglycinate ethyl; N - / - 5- (2 ', 4'-dichlorophenoxy) -

  Sec-butyl 2-nitrobenzoylglycinate; the N - / - 5- (2 ', 4'-di-

  propyl chlorophenoxy) -2-nitrobenzoylglycinate; the N-f 5-

  (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl-7-glycinate n-amyl;

  N-L-5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl-3-aminopropanol

  ethylpionate; N - / - 5- (2 ', 4'-dichlorophenoxy) -2-nitro-

  isopropyl benzoylglycinate; N - / - 5- (2'-chloro-4'-tri-

  fluorométhylphénoxy) -2-nitrobenzoyl7glycine; the N - / - 5- (2'-

  1-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl-37-glycinate

  sopropyle; N - 5- (2'-chloro-4'-trifluoromethyl) -2-nitro-

  methyl benzoylglycinate; N- (5- (2'-chloro-4'-tri)

  sec-butyl fluoromethylphenoxy) -2-nitrobenzoylglycinate; N - / - 5- (2'-Chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl

  ethyl alaninate; N - / - 5- (2'-chloro-4'-trifluoromethyl)

  ethyl phenoxy) -2-nitrobenzoyl7-) aminopropionate. Among these compounds cited by way of example, those comprising

  trifluoromethyl group on the Y-position of the general formula

  have proved to be particularly effective.

  It goes without saying that the stereoisomers and optical isomers of the compounds represented by the formula above

  in the context of the present invention.

  The compounds according to the invention are synthesized,

  in practice, for example by reaction of a benzene halide

  zoyl suitably substituted with at least a stoichiometric amount of an appropriately substituted amino ester, using techniques known to those skilled in the art. Substituted benzoyl halides and aminoesters

  substitutes can be obtained from commercial sources.

  or prepared by known techniques. More particularly, at least a stoichiometric amount of substituted benzoyl halide is added with stirring.

  substituted amino ester, preferably in the presence of a

  acid, such as, for example, triethylamine, pyridine

  ridine, N, N-dimethylaniline or the like. Given that

  the reaction is exothermic, benzoyl halide

  titué is added in fractions, so that the temperature

  of the reaction mixture does not substantially exceed about 55 C.

  One or other of the reagents that are the substituted benzoyl halide and the substituted aminoester, or both, may be dissolved if necessary in an inert solvent such as for example benzene, methylene chloride, chloroform ethyl acetate, tetrahydrofuran and the like. At the end of the addition of the substituted benzoyl halide, the reaction mixture is heated to reflux and is maintained there until the reaction reaches the desired degree of completion. The reaction mixture is then cooled to

  the ambient temperature and consecutively washed with

  diluted mineral acid, a dilute caustic solution and water, and subjected to phase separation. Diphenyl ether

  substituted is recovered from the organic phase by no

  o30 which known technique, such as for example

  crystallization, vacuum drying and the like. Substituted diphenyl ether as a product may be required

  be purified later, for example by recrystallisa-

  tion. Examples I to IX below illustrate the synthesis

  of certain compounds of specifically substituted diphenyl ether

  according to the present invention, but in no way limit it.

EXEMPLE I

  N - / - Ethyl 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate

  In a 100 cm3 balloon equipped with a light bulb

  of a reflux condenser and an agitator bar.

  Magnetic solution was charged with a solution of 1.03 g (0.01 mol) of glycine ethyl ester and 1.01 g (0.01 mol) of triethylamine in 25 cm 3 of benzene. The solution was stirred at room temperature and a solution of 3.450 g (0.01 mole) of 5- (2 ', 4'-dichlorophenoxy) 2-nitrobenzoyl chloride in cm 3 of benzene was added dropwise after what

  an exothermic reaction was observed. After the end of the ad-

  In addition, the mixture was stirred at room temperature

  2 hours, heated to reflux, maintained for two hours

  and then cooled to room temperature. To me-

  The mixture was transferred to a separating funnel and washed separately.

  each time with 30 cm3 of 1 N hydrochloric acid, water, 1 N sodium hydroxide and water. The organic layer was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. to a rust-colored solid.

  containing N-f-5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylgly-

  ethyl cinate. The solid was recrystallized in a

  minimum benzene content: ligrol (30:70 vol / vol); a crystalline tan solid was obtained consisting of ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate (yield 72%) with a melting point of 110-112 [deg.] C. a mass spectrum showing a molecular weight of 412 with

Fragments at 412, 310 and 236.

EXAMPLE II

  N - / - Methyl 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate. In a 100 cc three-necked flask equipped with a reflux condenser, an introductory funnel and

  magnetic stir bar, a solution was loaded into the

  0.89 g (0.01 mole) of glycine methyl ester and

  of 1 g (0.01 mole) of triethylamine in 30 cm3 of tetrahy-

  drofuranne. Although the solution was stirred at the same

  at room temperature, a solution of 3.45 g (0.01 mol) of chlorine

  of 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl in 20 cm3

  tetrahydrofuran was added dropwise / 8 observed

  exothermic heating. After the addition was complete, the mixture was refluxed with stirring for 2.5 hours, cooled to room temperature and then transferred to a separatory funnel. It was then diluted with 50 cm3 of ethyl acetate and washed separately with

  respectively 30 cm3 of 1 N hydrochloric acid, 30 cm3 of hy-

  1 N sodium hydroxide and 30 cm3 of water. The organic layer has

  was removed, dried over magnesium sulfate and then

  centered in a rotary evaporator at 55 C in a yellow syrup which crystallized at rest. The crystallized yellow material was then recrystallized from a solution of benzene and ligroin (30:70 v / v), which provided a solid

  swollen, tan color, consisting of N - / - 5- (2 ', 4'-dichlo-

  methyl r-phenoxy) -2-nitrobenzoylglycinate with a melting point of 133 to 135 ° C. and a mass spectrum showing a molecular weight of 398. 2.5 g of substance were obtained,

  corresponding to a yield of 63%.

EXAMPLE III

  N - / - 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate

butyl.

  2.06 g (0.005 mol) of N - / - 5- (2 ', 4'-dichlorophenoxy) -

  Ethyl 2-nitrobenzoylglycinate (prepared in Example I)

  were introduced into a 100 cm3 flask equipped with a

  refluxer and a magnetic stirring bar and then 0.4 g (0.01 mole) of sodium hydroxide

  cm3 of water. The suspension was stirred and heated

  flow until dissolution of the entire solid (approximately

  50 minutes), then for another 10 minutes. The

  the solution was cooled and 20 cm3 of a chloroacid solution

  Hydrogen to 10 were added. He had formed a solid tights. The mass was diluted with 50 cm3 of water and extracted twice with 50 cm3 of ethyl acetate. The extracts were

  combined, washed with water and then dried over sodium sulphate

  sium. The solvent was removed by means of an evaporator

  rotated at 550C and a light brown syrup of N - / - 5-

  (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycine, whose

  The mass ratio indicated a molecular weight of 384, with

fragments of 384 and 310.

  A solution of> .84 g of N / 5- (2 ', 4'-dichlorophenate)

  oxy) -2-nitrobenzoyl glycine (prepared as described above) and 0.35 g of phenolsulronic acid in 50 cm 2 of sec-butadiene.

  was introduced into a 10 cc flask which was

  linked to a Dean Stark receiver and was equipped with magnetic stirring. The solution was stirred and heated to reflux while the water was removed azeotropically. After about 26 hours of reflux, the solution was cooled and the sec-butanol was removed at 55 ° C using a rotary evaporator. The residue was dissolved in 50 cm3 of methylene chloride and the solution was washed twice with 30 cm3 of 1N sodium hydroxide and once with 50 cm3 of water. The

  The organic layer was then dried over magnesium sulphate

  and was concentrated in a rotary evaporator at 55 ° C. A light red oil was formed which crystallized on standing to yield a crude product consisting of N-Z-5- (2 ', -dichlorophenoxy) -2-nitrobenzoylglyoinate.

  sec-butyl. The raw product was recrystallized from a quantity

  minimum strength of a mixture of ethyl acetate and ligroin

  (25:75 vol./vol.) Warm, which formed a solid white

  N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate

  of sec-butyl with a molecular weight of 440, as determined

  mass spectroscopy, and fragments at 440, 367

and 310.

Example IV

  N-Isopropyl 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoylglycinate.

  A solution of 3.84 g of N - / - 5- (2 ', 4'-dichlorophene)

  nox -2-nitrobenzoylglycine (prepared as in Example III)

  and 0.35 g of phenolsulfonic acid in 50 cm 3 of isopropanol.

  panol was loaded into a 100 cm3 balloon equipped with a

  Dean Stark. a reflux condenser and a magnetic stirring bar. The solution was refluxed and the water removed azeotropically. After about

  2 hours of reflux, the solution was cooled and the

  buta.ol was removed by means of a rotary evaporator at

-2482589

   C, which gave a sticky solid. The solid was dis-

  under 50 cm3 of ethyl acetate and the solution was

  with about 30 cm3 of sodium hydroxide, then with water. The organic layer was then dried over magnesium sulfate and concentrated in a rotary evaporator.

  tif at 550C, which gave a solid of a white easse. The O-

  lide has been recrystallised in a minimum amount of one

  ethyl acetate and ligroin (25:75 vol./vol.) warm, which provided a white powder (3.1 g, yield

  73%) consisting of N - / - 5- (2 ', 4'-dichlorophenoxy) -2-

  nitrobenzylol glycylglycinate with a molecular weight of 426, as determined by mass spectrometry, with fragments of 426, 367 and 310 and a melting point of

99-100C

  Example V - [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl]

ethyl glycinate.

  The procedure of Example I was followed by this

  close to an equivalent amount of 5- (2'-chloro

  4'-trifluoromethylphenoxy) -2-nitrobenzoyl was used

  instead of 5- (2 ', 4'-dichlorophenoxy) -2-nitro-

  benzoyl to give N- (5- (2'-chloro-4'-trifluoromethyl)

  phenoxy) -2-nitrobenzoyl-7-glycinate ethyl.

Example VI

  N - / - 5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl7

ethyl alaninate.

  In a 100 cc three-necked flask equipped with an introduction funnel, a reflux condenser and a magnetic stirring bar, 1.4 g (0.012 mol) of ethyl ester were introduced. alanine and 1.1 g (0.01 mol) of triethylamine in 30 cm3 of benzene. To the stirred solution at room temperature (about 20 C), it was added

  dropwise 3.79 g (0.01 mole) of 5- (2'-chloro) chloride.

  ro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl in 20 cm3 of

  benzene. (The reaction mixture exhibited exothermicity).

  After the end of the addition, the mixture was heated with

  flow for 6 hours, cooled and then transferred to a separating funnel. It was then washed separately with

  each time 1 N hydrochloric acid, water, hydrochloric acid,

  1 N sodium hydroxide and water. The organic phase was then dried over anhydrous magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. to give 3.8 g of an oil.

  light yellow consisting of N - / - 5- (2-chloro-4'-trifluoromethyl)

  ethylphenoxy) -2-nitrobenzoyl-7-alaninate with an NMR (acetone, d6) 7.1-8.3 (multiplet, 7H); 4.55S (quartet, 1H); 4.15 (quartet, 2H) 1.25, (multiplet, 6H) The yellow oil crystallized at rest and the crystals

  had a melting point of 98-100 C.

EXAMPLE VII

  N - / - 5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl7

Ethyl 5-aminopropionate.

  In a 100 cc three-necked flask equipped with a feed funnel, a reflux condenser and a magnetic stirring bar was charged with 1.4 g (0.012 mol) of ethyl ester. of α-alanine and 1.1 g (0.01 mol) of triethylamine in 30 cm 3 of benzene. To the stirred solution at room temperature (about 20 ° C), 3.79 g (0.01 mole) of 2'-chloro-4'-trifluoromethylphenoxy-2-nitrobenzoyl chloride was added dropwise to the reaction medium.

  20 cm3 of benzene. (The reaction mixture exhibited exo-

  thermicity). After the end of the addition, the mixture was heated

  The mixture was refluxed for 6 hours, cooled and transferred to a separating funnel. It was then washed separately with each time 1N hydrochloric acid, water, 1N sodium hydroxide and water. The organic phase was then dried over anhydrous magnesium sulfate and then concentrated in a rotary evaporator at 550 ° C. to give 3.7 g of an oil.

  light yellow composed of N - / - 5- (2'-chloro-4'-trifluoromethyl)

  ethyl phenoxy) -2-nitrobenzoyl-3-aminopropionate with NMR (acetone, d6) 7.1-8.2 a (multiplet, 7H); 4.0f (quartet, 2H); 4,565 (quartet 2H) 3, 62Y (triplet, 2H); 1.28S (triplet 3H)

EXAMPLE VIII

  N - (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzyl

Sec-butylate.

  The glycinate prepared as indicated in the example

  V was hydrolysed and esterified according to the described procedure.

  described in Example III to provide N - / - 5- (2'-chloro-4'-

  trifluoromethylphenoxy) -2-nitrobenzoylglycinate

butyl.

EXAMPLE IX

  N-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzol

isopropyl lycate.

  The glycinate prepared as indicated in the example

  V was hydrolysed and esterified with isopropyl alcohol

  according to the procedure described in Example III,

  giving N - [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-

  isopropyl nitrobenzoyl7glycinate.

  Although the method of synthesis of the compounds according to the inventiorn has been illustrated in detail by Examples I to IX above, it is clear that any compound of the present invention can be prepared by those skilled in the art by simple change in the choice of raw materials

  and the use of illustrated techniques or any

appropriate standards,

  The compounds according to the invention have proved to be effective

  caces for regulating the growth of a variety of

  unwanted plants, namely weeds, when

  they are applied in an effective amount from the herbicide point of view. on the growth medium before the emergence of weeds or weeds after emergence of the growth medium. The term "effective amount of the point

  herbicide "refers to the amount of compound or compound

  A mixture of compounds necessary to damage weeds to the point that they are unable to recover after application. The amount of a particular compound or mixture of compounds applied to obtain a

  herbicide satisfaction can vary in a wide range of

  m-e and depe :: d various factors such as for example the

  the hardness of a particular weed species,

  depending on weather, climatic conditions, soil condition, method of application and the like. Typically, as little as 0.227 kg-or less per hectare up to 11.35 kg or more per hectare of compound or mixture of compounds may be required. The effectiveness of a particular compound against a particular weed species

  can of course be easily determined by a relative test.

  in the laboratory or in the field, according to a

  well known to those skilled in the art.

  The compounds according to the invention can be used as such or in a formulation with agronomically acceptable adjuvants - inert carriers. herbicides or other commonly used agricultural compounds, eg pesticides. stabilizers, protectors, fertilizers and the like. The compounds according to the invention,

  whether or not they are in formulation with other substances

  these agronomically acceptable, are typically applied in the form of dust, granules, powders

  wetting, solutions, suspensions, aerosols, emul-

  sions, dispersions and the like, in a manner well known to those skilled in the art. When formulated with other agronomically acceptable substances used

  typically, the amount of the compound (s) according to the invention.

  The present invention may vary in a wide range, for example from about 0.05 to about 95 weight percent of the formulation. In practice, such formulations

  contain about 5 to about 75? by weight of the cGm-

posed according to the invention.

  The compounds according to the invention have been found to be

  for the control of a variety of grassy and broadleaf weeds at application rates of 2.27 kg per ha or less, pre- or post-emergence, without significantly damaging desirable crops as per for example, corn, wheat, rice and soybeans. of the

  examples of weeds that can be effectively combated

  by the application of the compounds according to the present invention.

  field mustard (Brassica kaber); the eyellow

  foxtail "(Setaria glauca), the" crabgrass "(Digitaria sangui-

  nalis); the coffeeweed (Sesbania spp.); the "velvetleaf" he (Abutilon theophrasti); the johnsongrass (Sorghum halpense); the "barnyardgrass" (Echinochloa crusgalli); the jimsonweed (Datura stramonium); the teaweed (Sida spinosa); the volubilis

gardens (Roth) and the like.

  Some of the compounds prepared according to Examples I

  at IX were evaluated for their herbicidal activity against

  some species of weeds under conditions of

  Controlled boratory light, temperature and humidity.

  Selected weed seeds were planted in flat bins. For pre-emergence trials, the bins were treated with the selected compound immediately after seeding. For post-emergence tests, the trays were treated with the selected compound after a

  germination period of two weeks. The compound was

  plied on the bins by spraying a -com resolution

  placed in a solvent at the indicated application rates, the condition

  weed growth was noted and the toxic effect

  compound has been evaluated periodically after application

  tion. The following shows in tabular form the weed species (identified by their common name), the compound applied to the weed species (identified by reference to the example in which it was prepared), the rate of application of the compound (in kg per ha) and the fact that

  the application was carried out before or after emergence.

  In each of the previous trials, it was observed that all of the various weeds were destroyed

  or damaged beyond the ability to recover, in the

  20 to 24 days after the application of the compound

ticular.

  Although the invention has been described with force

  in connection with its illustrative embodiments

  it is understood that this does not limit it in any way.

Compound weed

I - VI VI VI VII VII

  Sorghum halepense X X X X X Datura stramonium X X X X X X Brassica kaber X X X X X Echinochloa crusgalli X X X X Sesbania spp. XXXXXX Abutilon theophrasti XXXXXX Roth XXXX Setaria glauca XXX x Digitaria sanguinalis (large) XXX Sida spinosa XXXX Xanthium X Application rate 11,35 11,) 3 2,2 2,27 2,2 '2,27 Emergence Pre Pre Pre Pre Pos Pre

248258-9

Claims (8)

  1. A compound, characterized in that it is by the formula: 0 R 0 ____ ,, X C_ N _R1 C-.NA -R2   wherein A is oxygen or sulfur; X is from   hydrogen or halogen; Y is a halogen or Urifluoro-   methyl; Z is a halogen or a nitro or cyano group; R is hydrogen or an alkyl group having from 1 to 4 atoms   of carbon; R 1 is an alkylidene group or an alkyl group   mono-substituted denen having up to 3 carbon atoms, wherein the substituent is an alkyl group having up to 4 carbon atoms and R2 is hydrogen, a group   alkyl containing up to 10 carbon atoms   bone, a cycloalkyl group having 3 to 8 carbon atoms,   or an agronomically acceptable ionic species.   2. Compound according to claim 1, characterized in   Y is trifluoromethyl or chlorine.   3. Compound according to claim 1, characterized in that R2 is an alkyl group containing up to 4 carbon atoms. 4. Compound according to claim 1, characterized in that R2 is an agronomically acceptable ionic species selected from alkali metals, alkaline earth metals, ammonium, an alkylammonium or an alkanolammonium containing up to 4 carbon atoms.   5. Compound according to claim 1, characterized in   what Z is a nitro or cyano group.   6. Compound according to claim 1, characterized in   what is selected from N - / - 5- (2 ', 4'-dichlorophenoxy) -2-   ethyl nitrobenzoylglycinate; N- [5- (2'-chloro-4'-tri)   ethyl N-ethyl 5- (5-ethylphenoxy) -2-nitrobenzoylglyeinate   (2,4-dichlorophenoxy) -2-nitrobenzoylglycine; the - N- / 5- (2'-   dichloro-4'-trifluoromethylphenyl-2-nitrobenzenesulfoyl; N - / - 5- (2'-chloro-4'-trifluoromethanesylphenoxy) -2-nitrobenzoyl glycinate isopropyl; the K -! - 52'r o   phenoxy) -2-nitrobenzoylglycinate of metnyl; the N - / - 5- (2'-   4-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoylglycinate   sec-butyl; N - / - 5- (2'-chloro-4'-trifluoromethylphenoxy) -2-   nitrobenzoyl 7 ethyl alaninate or N- [5'-chloro-4-tri]   fluromethylphenoxy) -2-nitrobenzoyl-3-aminopropionate ethyl.   7. Herbicide composition - characterized by an effective amount of herbicidal content   compound or a mixture of compounds according to claim 1.   8. A method of combating the growth of mis-   herbs, where a quantity of a herbicidally effective herbicide is applied to the growth medium before   weed control or is applied to the weeds   herbs after the release of the medium of growth, 3ara-   in that it includes the use and the   of, a quantity of the point of an effective herbicide of ir   compound or a mixture of compounds according to claim 1;