CS235509B2 - Herbicide agent - Google Patents

Abstract

The herbicidal diphenyl ethers are of the general formula I <IMAGE> wherein: A is halogen, cyano or nitro; X is hydrogen or halogen; Y hydrogen, halogen, cyano, trifluoromethyl, or C1-4 alkyl; Z is oxygen or sulfur; R is C1-3 alkylidene or monosubstituted C1-3 alkylidene, wherein the substituent is selected from C1-4 alkyl, C1-4 oxyalkyl or C1-4 hydroxyalkyl; and R<1> is hydrogen, alkyl or C1-10 alkoxy, C3-8 cycloalkyl, an agronomically acceptable ionic species, phenyl, or mono-, di-, or trisubstituted phenyl wherein the substituent(s) is (are) selected from halogen, C1-10 alkyl or C1-10 alkoxy, cyano, nitro, or trifluoromethyl, or an optical or stereo isomer thereof.

Description

The present invention relates to a herbicidal composition based on substituted diphenyl ethers which exhibits a herbicidal action.

which

In the prior art, substituted diphenyl ethers which exhibit herbicidal activity are well known, such as sec-butyl- (2-chloro-4-trifluoromethylphenoxy) -2- nitrobenzoate, of the following general formula, which is disclosed in U.S. Patent 3,798,276

It is an object of the present invention to provide herbicidal compositions which have superior efficacy.

The herbicidal composition according to the invention comprises a herbicidally effective amount of at least one compound of the formula I as active ingredient.

Y in which means

And bromo or nitro,

Y is hydrogen or halogen, k is alkylene or monosubstituted (I)

4 alkylene of 1 to 3 carbon atoms, said substituents being an alkyl, oxo or hydroxyalkyl group of 1 to 4 carbon atoms, and

K ¹ is hydrogen, C ¹ -C 10 alkyl, C 3 -C 8 cycloalkyl, agronomically acceptable ion, phenyl, monosubstituted, disubstituted or trisubstituted phenyl, said substituents selected from the group consisting of halogen, alkyl or (C 1 -C 10) alkoxy, cyano, nitro or trifluoromethyl;

Preferably, the herbicidal composition of the present invention comprises as an active ingredient a compound of formula (I) wherein A is nitro, Y is chloro, Ή is ethylene, and R ¹ is an alkyl group containing 1 to 2 10 carbon atoms or a cycloalkyl group containing 5 to 7 carbon atoms ·

The herbicidal composition according to the invention preferably contains, as active ingredient, 1-ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate or 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoate.

ben -эу halogen in v. ' ^л9

The herbicidal compositions of the present invention are effective in controlling the growth of various plants, i.e. undesirable plant species, such as various weeds. The compositions of the present invention are effective in controlling the growth of various broadleaf and grass-like weeds, both preemergence and postemergence applications can be used. The application of the herbicidal compositions according to the invention practically does not damage crops such as corn, wheat, rice, and soybeans.

eát -e

Examples of weeds that can be controlled when the compositions of the present invention are administered include the bloody dew, Chicory, abutilone,

Halloid sorghum, hedgehog, leg, durman, bladder, etc. The compositions of the present invention are effective for post-emergence application at relatively very low doses, such as, for example, 0.014 g / m ² ? ^{o <3ob} ' ^P '

In general, the invention relates to substituted diphenyl ethers exhibiting herbicidal activity, having the following general exemplary

Y (I *) in which a represents a nitro group,

Y is hydrogen or halogen, xt is an alkylene group or a monosubstituted alkylene group having 1 to 3 carbon atoms, wherein the substituent is selected from the group: alkyl, oxo or hydroxyalkyl having 1 to 4 carbon atoms, and

R ¹ is a hydrogen atom, a C 1 -C 10 alkyl group, a C 3 -C 8 cycloalkyl group, an agronomically acceptable ion, a phenyl group, or a mono-, di- or tri-substituted phenyl group in which the substituent or substituents are selected from: halogen, alkyl or C 1 -C 10 alkoxy, cyano, nitro or trifluoromethyl.

In a general embodiment also belongs to the group of the substituted diphenylether compounds výěe those compounds of formula (I ') in which stbsSituenty Y' and ^R1 К already ora ^h. Uve en ^{d Y are as} defined, ^p ři.čemž substituent A represents a bromine atom or a cyano group.

As an example, halogens mentioned above include, for example bromine, chlorine, iodine or fluorine, and preferably in a composition according to the invention uses an active ingredient of the above general model: ^ _ce> which contains as halogen bromine or chlorine . Examples of some of the alkyl and cycloalkyl groups mentioned above include, for example, methyl, ethyl, isobutyl, n-butyl, t-butyl, n-amyl, heptyl, octyl, isooctyl , noityl, decyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and the like.

Suitable alkoxy, oxo and hydroxy: alkoxyalkyl \ YMI groups include methoxybenzoyl xyskupina, ethoxy, butoxy, octoxy, oxoethyl group, o ^ opropylová group oxobutyl group, hydroxymeeylová and HY <fr <HXF ^e isopentyl, hydroxypropyl, a hydronyl group and the like. Examples of suitable alkylidene groups include methylidene, ethylidene or propylidene. Examples of the agronomically acceptable ionic elements mentioned above include alkali metals such as sodium, potassium or lithium, alkaline earth metals such as barium or calcium, ammonium ion or an alkylammonium ion or an alkanolammonium ion. containing 1 to 4 carbon atoms.

Examples of particular preferred active compounds, as active ingredients of the herbicidal compositions of the present invention, of the above formula are:

1- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1- (ethoxycarbonylmethyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-trifluoromethylphenoxy; (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitroisoizoate, 1- (ethoxycarbonyl) methyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzyl 2-uxuprupyl 5- (2-chloro-4-trifturelethylphinoxy) -2-nibobeis,

1 '- (ethoxycarbonyl) butyl (4'-chloro-4-trifluorophenoxy) -2-nitrobutylbutyl- (thinoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenox1) -2-nitro-benzoate (1- (3-Chloro-4-trifluoromethyl-phenyl) -propyl) -5- (2-chloro-4-trifluoromethyl-phenyl) -benzyl] -2-methyl-butyl 2-nitro-ethyl, (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifuran: methylphenoxy) -2-bromobenzoal, 1- (ethoxycarbonyl) -2'-hydroxy-prupyl 5- (2-chloro-4-trifluoroitinoxy) 2-nirroStizuát (etuxyksгbonn1) ety1 5- (2-cUlur-4-trifluoromethyl-methyl EROS) -2-kysnobenzoás, ^/ - (etoэyksrSorn1) ethyl 5- (2,6-iLcUlur-4-eno trifturett1lf ^ y) - 2-nitro-methyl-1- (ethylcarbonyl) ethyl] - (3-chloro-6-brue-4-trifluoromethylphenoxy) -2-nitro-benzoate,

It is also understood that the present invention includes the stereoisomers and optical isomers of the active compounds as components of the herbicidal compositions of the invention.

of the active compound. herbicidal prostředků.podle invention, the above general model (^ i'ce are prepared by reacting the appropriate substituovθnéUu benzoylhslogenidt of formula (H), wherein J and _E set forth štbstLtteit wherein M is a halogen atom, with an alcohol or ^ y ^ with suitable The substituted (III) -substituted hydroxylic acid ester of formula (III) below, wherein Q is -OH, or by reaction of a suitable substituted benzoic acid of formula (II). ) in which it is a substuene

AND.' the OH group is suitably substituted with an alpha-halo-spiroxylic acid ester of formula (III) in which the substituent Q is halogen using known synthetic procedures and the reaction scheme is as follows: ujíc ^:

23> 509 (II)

O

N -CI (I) wherein one of M or Q is halogen and the other is -OH.

Said benzoyl halides (or acids) ^and substituted esters of hydroxyhydroxy (or alpha-halogen) carboxylic acids may be obtained. from commercially available starting materials, or may be prepared by known methods. Specifically, at least a stoichiometric amount of substituted benzoyl halides is added from the stirring to the stabilized alpha-hydroxycarboxylic acid, preferably in the presence of an acid binding agent such as triethylamine, pyridine, Ν, H- dimethylanone, or the like.

Since said reaction is usually exitermická, substiuuovaný benzoyl halide must be added after mmlých portions that the temperature did not exceed srnměl pMliS 'at about З ^fifth Deň: 32 ° C. Ш ^{p p} rav of manufacture ^of composites herbicldnteh punched ^{ou p} nstřed invention by reacting the substituted benzoic acid with an alpha-halocarboxylic acid in the preferred embodiment the second substance is added to said first substance in said přítomnnoti azoslltčeoioy such as 1-э dilZlbicykll- (5,4,0) uodec-5-eo (DHJ). Alternatively, the reaction may optionally be carried out in the presence of an inert solvent such as benzene, methylene chloride, chloroform, ethyl acetate, tetrachloride, or the like. substances.

Upon completion of the addition of the substituent-1-beozoyl-β-genide to the εΙΙ-ΙΙ ^ ^γοο (x neboyl ester ester ester (nebo ((nebo (or after the addition of the alpha-θθlogengengenkarblblbl kS ester k k k k k k k k k k k k k k k k k k k se se se se), the reaction mixture is heated to reflux. The reflux condenser is maintained until it reaches the desired degree of conversion. The reaction mixture is then cooled to ambient temperature and is usually washed successively with dilute acid, dilute basic compound and water and then allowed to phase separate. The substituted diphenyl ether is recovered from the organic phase by any known method, such as by evaporation, capitalization, vacuum drying, or the like. If desired, the recovered product, i.e., the substituted diphenyl ether, can be further purified, for example by recycle / sensation.

The herbicidal compositions of the present invention are effective in controlling the growth of various undesirable plants such as those mentioned above, such as various weed species, when applied in an herbicidally effective crop to the area in which the weeds are grown, either pre-emergence or post-emergence. The term herbicidally effective m ^ CFCs ^ knows that was used sho ^ refers mnlžtví ^account IOO ^with sL · ^ ¹ or SMe ^ l ^ irný ^ ^ OTE ^{0 to} TER% miscarriage ^b n ^with complete destruction or damage weeds to the extent that the weed is then no longer capable of emerging after application. The amount of individual active compounds or mixtures of active compounds which are applied to obtain a satisfactory healing effect can vary considerably over a wide range and depending on various factors, such as the persistence of the uniform weed species, the weed infestation rate, climatic conditions, soil conditions, method and the like. It is usually used according to the invention

the small amounts of the active compounds of the herbicidal compositions according to the invention or mixtures of these active compounds, the amount usually being in the range of. 0.22 kg / ha to 11.1 kg / ha. It goes without saying that the efficacy of individual active compounds against individual weed species can be readily determined by direct laboratory or field testing, which can be accomplished by known methods. .

The herbicidal compositions of the present invention may be used as such or in admixture with agronomically acceptable additives, carriers, other herbicidal compositions or other commonly used agricultural compounds such as pesticides, stabilizers, fertilizers and the like. Herbicidlí means ccording mentioned ^{e p} his invention, whether j ^Iz Smee in other agronomically adopted ^ Mi ^and ERI ^AL y or without them, are usually administered as a dust, a grant !, ^^ sm powders by phone, solutions, suspensions, , aerosols, emulsions, dispersions or the like, by methods well known in the art.

When the herbicidal compositions of the present invention are mixed with other commonly used agronomically accepted compounds, the amount of active compound or compounds in the herbicidal compositions of the present invention is in a wide range, for example in the range of about 0.05 to about 95% by weight Generally, these compounds contain the active compound or compounds in a range of from 5 to about 75% by weight.

The herbicidal compositions of the present invention have been shown to be:. They are effective in controlling various weed species and grass weeds, and at rates of application ranging from 2.2 kg / ha to lower levels, both pre- and post-allergenic applications can be used. In these applications, virtually no substantial destruction of cultivated crops, such as, for example, corn, wheat, rice and soybean, will occur.

Examples of weeds which can be effectively controlled by the application of the herbicidal compositions of the present invention are the following species: mustard (Braasice kaber), yellow rams (Setarie glauca), bloodwort (Digitaria sangumaiiU, chicory (Sesbania spp ·), abutilon ( And a trillion thropPrrrSiL, or the year of the dormant (Sorghum halepense), the hedgehog, the chicken leg (Echinochloa cruugaaii), the common durman (Datura strunium, Side spinosa, annual or high (Roth) and the like).

The following Examples 1 to 12 illustrate a process for synthesizing certain specific batik diphenyl ether compounds as active ingredients of the herbicidal compositions of the present invention.

Peak 18 d 1

Preparation of 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylthioxy) -2-nitro-phenol

In a 100-liter three-necked flask equipped with an additional funnel and a reflux condenser and a moagitic stir bar, 1.18 g (equivalent to 0.01 µol) of etillactate e 0.79 g (equivalent to 0.01 uol) pyridine in 30 [mu] l of tanzene. ^To this solution, 3.79 g (corresponding to 0.01 µmol) of 5- (2-chloro-4-trifluoromethylphenyl) -2-nitro-benzylchloride was added dropwise thereto from the trench temperature (about 20 ° C). in 20 ol of benzene. An exothermic reaction then takes place. After the addition was complete, the reaction mixture was heated to reflux temperature and maintained at this temperature for 6 hours. The reaction mixture was cooled, transferred to a separatory funnel, and 30 ml portions of 1 N hydrochloric acid, water, 1 N sodium hydroxide and water were successively passed through. The washed organic phase is then dried with magnesium sulfate and then concentrated by rotary concentration. Evaporator at> 5 ° C

23р509 to give 2.89 g of a light yellow oil which was identified as 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate, the analysis of which was as follows:

Ha (acetone, Dg): 7.3 to 8.3 delta (complex · muUtiplet, 6H), 5.35 delta (queaOelt, H), 4.28 delta (quaret, 2H), 1.62 delta (dubbet) (3H), 1.25 (triplet, 3H).

Example 2

Preparation of 1 '- (ethoxy-cyclohexylmethyl) -ethyl 5- (2-chloro-4-trilino-4-ethylamino-phenyl) -2-oxo-benzo [not]

According to this embodiment the procedure is such that in _ч 1O0miliiiioové necked flask which is equipped with an addition funnel, reflux kondenzátoree e · eegnetickýe stirrer, was charged with 1.32 g (0.01 MEL) 3 hydooxybutyráiu acetate and 1.1 g ( To this stirred solution is added dropwise 3.69 g (corresponding to 0.01 mol) of triethylamine in 30 ml of benzene at ambient temperature (about 20 DEG C.). mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 20 ml of benzene. After the addition is complete, the reaction mixture is warmed to room temperature and maintained at this temperature for 6 hours.

The reaction mixture is cooled, transferred to a separatory funnel, and finally 30 ml portions of 1N hydrochloric acid, 1N sodium hydroxide and water are successively dried. The washed organic base is then dried over magnesium sulphate and concentrated. Concentrate on a rotary evaporator at 55 ° C to give 3.75 g of brown gum that was identified as: 1 * - (ethoxycarbonylmethyl) ethyl 5- (2-chloro-4-trifluoromethylene): χy) -2-nitro-benzoate, the analysis of which is as follows:

NMR (acetone, dg): 7.2-8.3 .delta (commpex, 6H), 5.5 .delta (quartet, 1H),

4.15 delte (quartet, 2H), 2.75 delte (dubbet, 2HT, 1.3 delta (dubbet exceeding triplet, 6H) · λ

Example · 3

Preparation of 2'-Carbonethyl 5- (2-chloo-4-trifluoroailiphenoxl) -2-nitrobenzoate

2.70 g (corresponding to 0.03 moles) of 3-hydroxypropionic acid and 2.38 g (corresponding to 0.03 moles) were charged into a 250 ml 3-necked flask, additional funnel, reflux condenser, and mmagetic mixing rod. corresponding to 0.03 mole) of pyridine in 110 ml meetlenchloridu · Respective stirred solution was then added at okoH ^{(i.e., P} s te ^ OTE about 20 ° ^{C) C} o ^p ka sPectrum ^11.37 g ^(from which ^p ovide °, ° ³ mole) of 5- (2-chlorophenyl) .oo-4-trifluoromethyl jooeletliaenoэy) -2-niOoobeezollchlooidj in 30 ml maillaechlooidu · in this Lázi is observed exotherm · After complete addition, the reacting mixture was heated to reflux and · Then held at this reflux temperature for 22 hours. The reaction mixture was then cooled, transferred to a seed funnel, and twice twice with 1% aqueous hydrochloric acid and once with 10 ml of water. The pierced organic bath was then dried over magnesium sulphate and concentrated on a rotary evaporator at 55 ° C. ° C to give 11.8 g of a viscous yellow oil which was identified as 2'-ethyl-3-olobolyl 5- (2-chloro-4-thiophenol) -4-thiolooyl-2-eto-benzoate, the analysis of which was as follows.

uv id uvtNMR (acetone, dg) ·: 7.2 to 8.4 delta (corplex, multiplet, 6H), ^{4.3 d} e-lte · Mplet, 2H),

2.67 ^d Elia ^{(triple-2H). a genius} of about 2 s.

Example 4 (ethoxycarbonyl) ethyl) - (2-chloro-4-trifluoromethylphenoxy) -1-nitrobenzoate

In this example, 20 ml of ethanol and> ml of pyridine in 30 ml of ethylene chloride are charged in a 100 ml three-necked flask, an additional funnel, a reflux condenser and an unethical stir bar. To this stirred solution is added at a temperature (about 20 ° C) in a longer phase, dropwise 2.26 g (corresponding to 0.00> moles) of 2 * - (chlorocarbonyl) - 6? 5- (2-chloro-4-trifluoromethylphenyl) -2-nitro-benzoate in 1; ml of letyltechloride. Upon completion of the addition, the reaction mixture was heated to reflux temperature and maintained at this reflux temperature for 42.5 hours.

The reaction mixture was then cooled and concentrated in a longer time using a rotary evaporator at> 5 ° C. The concentrated residue is then taken up in 100 ml of methyl technoid, the mixture is transferred to a separatory funnel, and then 30 ml of 1N hydrochloric acid, water, 7% aqueous ammonium hydroxide solution are successively washed. and water. The pore-washed organic phase is then dried over magnesium sulphate and finally concentrated on a rotary evaporator at 55 ° C to give 1.3 g of a yellow oil which has been identified as: 2 '- (ethoxycattoxyl) ethyl 5- (2). (chloro-4-trifluoromethylphenyl) -2-nitro-benzoate, the analysis of which is as follows:

NMR: (chloroform) 7.0-8.1 .delta. (.Delta., 6H), 4.3 .delta. (.Delta., 4H), 2.65 .delta. (Triplet, 2H), .delta. (triplet, 3 H).

Example 1 and d 5

Preparation of 1 '- (Eloxycarbonyl) mmyl 5- (2-chloro-4-yl) fluoromethylphenyl] -2-methyl ester acetate

According to this embodiment, 1.25 g (equivalent to 0.012 mol) of ethyleacetyl glycolate and 0.80 g (equivalent to 0.01 mol) were charged into a 100 liter liter vessel equipped with three orifices, an additional funnel, a return coedezer and a stir bar. ) pyridine in 3? ml of Leeyl Chloride To the stirred solution of the above components is added dropwise 3.79 g (corresponding to 0.01 moles) at 0 DEG C. (i.e. 20 DEG C.), dropwise. 4-Chloro-3-trifluoromethylphenoxy) -2-nitro-benzol chloride in 20 ml of methyl chloride (at this point an exothermic reaction was observed).

After complete addition, the reaction mixture 'is heated to reflux and at this temperature was maintained for 42 hours _t i. · In another reaction mixture was cooled, transferred to a separatory funnel, and sequentially rubs 30mililitoo'ýmL portions of 1N HCl, water, 7% aqueous ammonium hydroxide solution and water. The simple organic phase is then dried over magnesium sulphate and concentrated in a rotary evaporator at 55 ° C for a long time to give 3.5 g of a yellow oil which is identified as 1 '- (etonycarbonyl) methyl. -chloro-2-methylbenzyl) -2-ethylbenzoate, the analysis of which is as follows:

ICEk (chloroform): 7.0-8.4 delta (muttppet, 6H), 4.82 delta (2H), 4.25 delta (quartet, 2H), 1.31 delta (triplet, 3H).

Example 6

Preparation of 1 ' -ethoxycarbonyl-2 ' -oxopropyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate.

The reaction scheme according to which this preparation is carried out is as follows:

Cl I СНзСО — СН-COOEt +

In this example, 3.61 g (corresponding to 0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) was charged into a 100 liter three-necked flask with an additional funnel and an unethical stir bar. 1-nitro-benzoic acid and 1.53 g (corresponding to 0.01 mole) of 1,5-diazobicyclo (5.4.0) -2.0-5.6- (DBU) in 50 ml of benzene. To this stirred solution at ambient temperature (i.e., at about ⁰ ° ^{с 2)} při.d ^and 1.6 ⁵ g ^(What answer ⁰ ° 1 lu m ^{^)} ^ Chloro-e ^ acetoecetátu winding. The reaction mixture was then heated to reflux and maintained at reflux for 20.5 hours. The reaction mixture was then cooled, transferred to a separatory funnel, and successively washed with 1N hydrochloric acid, water, 7% aqueous ammonium hydroxide and water.

The washed organic phase was dried over magnesium sulphate and then concentrated on a rotary evaporator at 22 ° C to give 3.1 g of a brown oil, which was identified as 1'-ethoxy-18 -boel-2-oxopropyl. - (2-Chloro-4-trifluoroethylphenyl) -2-nitro-benzoacetate, the analysis of which is as follows:

NMR (acetone, dg): 7.2-8.2 Ut (Utiplet, 6H), 5.8 ((singlet, 1H), 4.2 ta (quartet, 2H), 2.3 te / singlet, 3H .

Example 7

Preparation 1 *) · ^(r eCoJyiet0cxn l) 0utyl 5- (2-4-chlct tríflotlletyífenoзy) -2-nitcobθnzcáil

In this example, a 3.61 g (equivalent to 0.01 mol) of 5- (2) was charged into a 100-ml, three-necked flask, an additional funnel, an additional condenser and a mahogany rod. chloro-4-trifluoromethylphenoxy) -2-nitro-benzoic acid and 1.53 g (corresponding to 0.01 mol) of DBU in 50 ml of benzene. To this stirred solution was then added at room temperature 2.19 g (corresponding to 0.01 mol) of ethyl 2- (2-methyl-2-methyl-2-methyl-2-methyl-ethyl). The reaction mixture was then heated to reflux temperature and maintained at reflux temperature for 22 hours. The reaction mixture was cooled, transferred to a separatory funnel and treated successively with 30 ml portions of 1N hydrochloric acid, water, 7% aqueous ammonium hydroxide and water. The simple organic phase is dried over magnesium sulfate and finally concentrated on a rotary ares of ^{P when} U at -Temperature »° C, ^to ignite in 2.2 ^{g of} a brown oil which was identifklcován as i '- (eoo3y carbonyl (1) butyl 2- (2-chloro-4-trifluoroethylphenoxy) -2-nitrobenzoate, the analysis of which is as follows:

NMR (acetone d 6): 7.2-8.2 delta (multtplet, 6H), 5.25 delta (triplet, 1H), 4.28 delta (quartet, 2H), 0.8-1.9 delta ( multtppet, 1CH).

Example · 8

Preparation of 1 '- (Phenoxycarbonyl-ethyl-5- (2-chloo-4-trifluoromethyl-phenyl) -2-methyl-benzyl)

According to this embodiment, a 100 ml vessel equipped with three orifices, an additional distribution funnel, a reflux condenser and a magnetic stir bar is charged. 3.61 g (corresponding to 0.01 mol) of 5- (2-chloro-4-trifluoromethylleenoxy) -2-isoobenzonic acid and 1.53 g (corresponding to 0.01 mol) of DBU in 50 ml of benzene. . To this stirred to flow and when ^p te ture surroundings ^(that in · means ко И about ²⁰ ^ ^с bow ^and

2.29 g (corresponding to 0.01 mol) of phenyl 2-bromoacetate.

The reaction mixture was heated to reflux and maintained at reflux for 22.5 hours. This reaction mixture. The mixture was then cooled, transferred to a separatory funnel and then treated with 30 ml portions of 1N hydrochloric acid. . water, 1N sodium hydroxide solution and water. PROBYT organic phase was dried over magnesium sulfate and further zkoncenXruje rotary evaporator at te ^p ture of 55 ° C, ^{and the} holding result of the personal identification Ostu ^{p p} u is ^2.58 grams of a pale-ciated with ^ upovrté materials in liquid form, which has been found ^to be 1 * - (phenoxylbenzil-ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrooleate), the analysis of which is as follows:

NMR (acetone, d 6): 7.0-8.25 delta (muutiplet, 11), 5.5 delta (quartet, 1H), 1.68 delta (doublet, 3).

Example 9

Preparation of 1 * - (enyloxycarbonyl) -lyl-5- (2-chloro-4-triflooiletylphenoxy) -2-benzenesulfonate

In this example, 3 to 61 g (equivalent to 0.01 mole) of 5- (2-chloro-4) are charged into a 100-mL vessel equipped with three orifices, additional funnel, reflux condensate and magnetic stirrer. Trifluoromethylphenyl) -2-nitro-benzoic acid and 1.53 g (corresponding to 0.01 mol) of DBU in 35 µl of benzene. To this stirred solution at that ^^ ^ ott surroundings ^(What is the neighborhood of about 2 ° °) p ^Rida dropwise 1.95 grams (0.01 mole) eίyl 22b0ooibutyoάtu · 1 in 5 ml of benzene. Exothermic heating of the reaction mixture takes place at this stage.

After the addition is complete, the reaction mixture is heated to reflux temperature and maintained at this reflux temperature for 24 hours. The reaction mixture was cooled, transferred to a separatory funnel, and washed successively with 30 mL portions of 1N hydrochloric acid, water, 7% aqueous ammonium hydroxide solution and water. The washed organic phase was then dried over magnesium sulfate, zkoncenitruje the ro ^ abdominal o ^ ataváku ^p s 55 ° C, ^the rice ^{from p} Ostu ^are converted to obtain ^{and 1,} 2 ^{g of} a light brown syrupy kejpaliny, which was identified as the 1 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitrooleo-o-carbonyl-4-trifluoromethyl-benzoate, the analysis of which is as follows:

NMR (acetone, d 6): 7.2-8.2 δ (multi δ) δ (δ t, δ), 5.15 delta (triplet,), 4.2 delta (quartet, 2H), 1.9 delta (quartet, 2H), 0.8-1.3 delta (overlapping triplets, 6H).

23> 509

Example 10

Preparation of 1'-Ethoxycarbonyl-3'-methylbutyl. > - (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate

1.60 g (equivalent to 0.01 mole) of ethyl alpha-lyrdroxyisocepronate and 0.79 g are charged into a 100 ml three-necked, three-necked flask, an additional funnel and a stirrer bar. (equivalent to 0.01 mole) of pyridine in 40 mL of methylene chloride. To this stirred solution is added from stirring at ambient temperature (i.e. at about 20 ° C), dropwise 3.79 g (corresponding to 0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) - Of 2-nitrobenzoyl chloride in 10 ml of methylene chloride. At this point, an exothermic reaction was observed. After the addition is complete, the reaction mixture is heated to reflux temperature and maintained at this reflux temperature for 46.5 hours.

The reaction mixture was cooled, transferred to a separatory funnel, and washed successively with 25 ml portions of 1N hydrochloric acid, water, 3.5% aqueous ammonium hydroxide and water. The simple organic phase is then dried over magnesium sulphate and concentrated in a rotary evaporator at a temperature of> 5 ° C to yield 3.99 g of a viscous brown going identified as 1 ^of -thoxycarbonyl-Z ^from -uutylbutyl 5. - (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzzoate, the analysis of which is as follows:

NMR (acetone, dg); . 7.2 to 8.3 delta (ralttplet, 6H), 5.2 delta (triplet, 1H), 4.2 delta (quartet, 2H), 1.8 delta (muuttppet, 3H), 0.8 to 1, 4 Delta (Muuttppet, 9H.

Example 11

Preparations 1 © '-etoxyirrbonyl-2 ^/ -hydroxyliΌlyl 5- (2-chloro-4-trifluoromethyl lormttyPeenoэy) -2-ntroobθnzoStl

A 500 ml flask equipped with three orifices, an additional funnel, a reflux condensate and a magnetic stir bar was charged, and 19.56 g (corresponding to 0.04 moles) was charged into the flask. -butoxycarbrol-2'-oxopropyl 5- (2-chloro-4-trifluoromethyl-5-thieno [eta] &lt; 5 &gt; -2-oxo) -benzoate ( This material was prepared as in Example o) in 100 ml of Meeanol. The stirred solution was then added at ambient temperature (i.e. about 20 ° C), 3.14 g (corresponding to about 0.05 moles) of sodium cyanoborohydride and a few drops of methyl indicator. In a further procedure, a 75:25 by volume mixture of 2N hydrochloric acid and methanol is added dropwise, the addition being carried out at a level sufficient to maintain the color of the indicator.

The reaction mixture was then heated to reflux and then maintained at this reflux temperature chlediče for 20 hours, ^further treatment e the mixture is cooled up ^to oncen0rlje on rotary about ^dp ares ^to u when t ep ^{l you} about 55 ° ^C. The obtained concentrated ^to a residue is then taken up in 200 ml of diethyl ether, transferred to a separatory funnel and washed consecutively lOOoiHlitrotymi poddly 1N hydrochloric acid, water, 1N NaOH and again with water. Simple organic phase is dried over magnesium sulphate and pnmool then zkoncenOruje rotary from ^P: Rovai ^to u ^p s te rt ^{pl of 55} ° C. The result of this example embodiment is 18.1 g of yellow, syrupy ka ^p Aline nape which are identified as 1 '-eoo3ykarbonyl-2' -hyclroxypropyl 5- (second-Chloro-4-triflooraetyifenoxy) -2-oitrobeozoát whose analysis is following:

IC.'ř <(acetone, d _b): delta 7.2 to 8.3 (muuttppet, 6H); 4.2 (muutippet, 3H), 3.2 delta (kvarret, 2H), delta 1.3 (dubUet overlay triplet, 5H).

1

Example 12

Preparation of 1 '- (ethoxycartornllethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoate

The process is carried out by placing 1.18 g (corresponding to 0.01 roles) into a 100 ml flask equipped with a throat, an additional funnel and a reflux condenser and an agitator. of ityl lactate and 0.79 g (corresponding to 0.01 mole) of pyridine in 50 µl of relyl chloride. To this stirred solution is then added dropwise 2.07 g (corresponding to 0.005 mol) of 5- (2-chloro-4-trifluoromethyl) oxy) -2-tooobenzoyl chloride in 10 ml of relylchloride at ambient temperature (about 20 ° C). At this stage, an iooteiraic reaction may be observed.

After the addition is complete, the reaction mixture is heated to reflux and maintained at this reflux temperature for 66 hours. The reaction mixture is then cooled, transferred to a separatory funnel and then washed successively with 30 ml portions of 1N hydrochloric acid. Water, 7% aqueous ammonium hydroxide solution and water. The simple organic phase is then dried over magnesium sulphate and concentrated on a rotary evaporator at 55 ° C. of a yellow syrupy liquid which has been identified as 1- (ethoзyiatbocfУlethyl 5v (22-chloro-4-trifluoromethylpyrroleoyl) 22-toorblphzoate, the analysis of which is as follows:

NMR (acetone, dg): 7.0 to 8.0 .delta. ([Delta] 161.6H), 5.25 .delta. (Quartet, 1H), 4.18 .delta. (Doublet, 3H), 1.68 .delta. , 1.18 (triplet, 6H) ·

Although the procedure for synthesizing the active ingredients of the herbicidal compositions of the present invention has been described in the previous Examples 1-12, it is obvious that any compound within the scope of the present invention can be prepared in a similar manner simply by varying the starting materials. I shall use the same procedure or any other alternative procedure that applies to it. well known in the art.

Some of the compounds prepared according to Examples 1 to 12 above have been tested for herbicidal activity against various weed species under controlled laboratory conditions such as light, temperature and air humidity. · In the case of the pre-emergence test, the containers were treated with selected compounds after the beginning, and in the post-emergence test, the containers were treated with selected compounds after a two-week * glacial interval · Herbicidally active compounds were applied to these containers by spraying solution of the compound in a given applied layer, with the growth of tulle weeds being monitored and the toxic effect of the tulle compounds evaluated periodically after application.

The following table shows the results of the test, the weed names being given the generic name, and the compounds applied in each case are indicated by the symbol 'X' * ', also indicating which example the compounds were prepared. compounds applied ptelrgenenér way in multiplication! 2.2 kg / ha ·

235509 12

Table

Weed 1 2 Compound 8 9 «С 4 7 O 7 Sida spinosa X X X X durman obecný X X X X X X X X X mustard deaf X X X X X X X X yellow tails X X X X X X X X rosička krevavá X X X X X X X X Sorghum X X X, X X X X chicory X X X X X Abutilon X X X X X povijnice vysoká X X X X X oat deaf X X X hedgehog corns the leg X X X X X X

In all of the foregoing tests, it was observed that all of the weed species were either destroyed or damaged without re-emerging at 2 to 22 days after application of the individual compounds.

In the following table, certain compounds were applied post-emergence nn certain weed species at a rate of 2.2 kg / ha.

Table

Weed 1 Compound 10 2 3 4 5 6 7 8 9 Sida spinosa X X X X durman obecný X X X X X X X X X mustard deaf X X X X X X X X X X yellow tails X X X X X X X rosička krevavá X Sorghum X X X X Chicory _w X X X X X X X X X X abutilon X X X X X X Povijnice vysoká X X X X X X X X X oat deaf X X X X hedgehog corns the leg X X X řepen X X X X

In all of the above tests, it was observed that the various weed species were either destroyed or damaged to such an extent that they did not reappear after an interval of 21 to 22 days after application of the individual compounds.

After carrying out the tests, it was found that the active compounds of the herbicidal compositions according to the invention in which the substituent A is a group other than a nitro group, for example a halogen atom and in particular bromine (as for example for the compound prepared according to Example 12) in the case where they are applied post-emergence as compared to the pre-emergence application, ^c at an application rate which is below about 5 - 5 kg / ha, for example about 2.2 kg / ha or even less. The herbicidal compositions of the present invention, containing active compounds in which the substituent A is a nitro group, are effective in both the pre-emergence and post-emergence applications at the application rates of 2.2 kg / ha or meetos.

The present invention has been described in sufficient detail with the aid of a number of practical examples, and it is to be understood that the scope of the present invention is not limited to the various embodiments of the present invention, but various alternative modifications are possible within the scope of the present invention.

To compare the herbicidal activity of the compounds, i. The active ingredients of the herbicidal compositions of the invention exhibiting the herbicidal activity of the invention with the prior art compounds were carried out by the following tests.

The following compounds were tested:

A. 1- (Tethoxycarbosyl) ethyl 5- (2-chloro-4-trifluoromethylphenyl) -2-nitsobenzyl-St, a compound of the foregoing. of the invention having the following general formula:

B. seto-butyl 5- (2-chloro-4-trifluoromethylene-oxy) -2-nitro-benzyl, which is. the prior art compound disclosed in U.S. Patent No. 3,798,276 of the following general formula:

Each of these compounds was dissolved in a 90: 8: 2 by volume mixture of acetone, methanol and dimethylformamide, and these were applied both pre-emergence and post-emergence to a variety of weeds that were grown in suitable containers under old controlled laboratory conditions. lighting, temperature and humidity.

The techniques used in pre-emergence and post-emergence treatments, the application of test compounds, and the evaluation of the effect of test compounds, as discussed below, are consistent with conventional testing and evaluation of herbicidal chemical compounds in research laboratories.

Pre-emergence treatment.

The soil medium used in the pre-test was a pasteurized mixture consisting of 3 parts of sandy, clayey top soil and 1 part of coarse grains of cement and sand, washed and sieved on a 0.476 cm sieve. Enough mirrors have been added to this growing environment! NPK fertilizers 5-10-10 to achieve the required nitrogen utilization rate of 0.011 2 kg / m ^c . Sufficient lime was also added to the medium to adjust the pH of the composition to 5.8-5.5. No other additives, such as, were used in the tests. if it is used, peat, clay, organic material or pellet, not used, these substances could lead to

23 »09 changes in the binding capacity of soil colloidal substances and thus changes in the potential efficacy of the applied compounds.

A container measuring 27.94 cm x 27.94 cm x 6.35 cm is filled up to a height of 0.95 cm from the top edge of the soil mixture, whereby the surface is leveled and compacted · Selena or plant parts of the desired weed species are then slightly It is pressed into this soil and then overlaid with a layer of sand sieved through a standard sieve # 8, the layer of sand being at the level of the upper part of the container. In the treatment of this soil, the surface is dry to reduce the possibility of degradation of the test compounds used, which are then incorporated into the soil at the same time as the first irrigation performed immediately after application of the test compounds.

The treatment is carried out.

The cultivation environment used in the post-emergence testing was a scarab mix of the weed species desired in individual pots of > 71 cm x 7.62 cm x 5.7 cm, the tulle seeds spread in the pot and overlaid with ρг-žtře. Regarding the state of physiological development, the broad-weed must have at least a real deer leaf and the grass weed must have at least three leaves before application of the tulle compounds tested.

Jednctlivé containers with different weed species were moved on the plate and were irrigated before application testovených compounds to the extent that all of the linseed plants tulle ^p o and t ^{y y} a ^d ceo ou ^at what bytes ^from its leaves dry. BIST ^{- ts} for ^{D with} test compounds or immediately after - the test compounds was additionally introduced into the soil solution at a concentration of 100 ppm of available nitrogen and the occiput pouSits Peters-soluble fertilizers 2C 20-20 purpose of delivery of nutrients needed for a three-week test period .

Application of test compounds.

Test compounds tulle applied to the plants in containers by spraying with a stably positioned jet sprayer above the moving belt. This sprayer was equipped with a flat spray cone nozzle equipped with a 50-mesh screen and a non-return valve. The nozzle was operated at a pressure of 10 psig, delivering 25 ml of dewatered water at a rate of 4.6 seconds and producing a spray of 45.72 cm wide at a distance of 25.4 cm above the surface. soil. The movement of the belt was controlled in such a way that the vessel passed under the nozzle at an interval of 4.6 seconds. Since the area wetted by p at this interval is 0.63 m *, the volume of the liquid used for irrigation is 39.84 ml / m.

After application of the test compounds, the vessels are swept into the cultivation chamber, whereby the growth status of the plants is periodically recorded and the effect evaluated. The 7 m x 7.62 m cultivation chamber was illuminated with a total of twenty 1,000 watt high-intensity discharge lamps mounted in a means of restraint equipped with mirror reflectors having a diameter of > height to produce an overlapping light spectrum at the base surface level. The illumination intensity of about 26,900 lux at baseline level. . The temperature in the cultivation chamber was maintained at 2⁸,⁸⁸ ° C to 3 ° C in the interval of a new pertet, when the tulle was illuminated and during the night this chord was kept at 21 ° C.^{, 1} Noc: 2 ° C 23^,Low: 14 ° C. Relative humidity in this growing^tožm)^žře is filled with lessⁿE^of 1 /³ tyla^and50 to 55 percent.

Evaluation of efficacy of test compounds.

The herbicidal activity of the test compounds was evaluated in the usual manner at 12-14 days and 20-22 days after application of the test compounds. The potency of the test compounds was evaluated in comparison to the control weeds, which were the same weed species grown in the same pots, and treated with the equivalent amount of vehicle solvent as applied to the test plants. The herbicidal activity of the test compounds on said weed species was determined by visual inspection of the plants and determining a value on a numerical scale indicating the degree of plant damage (NIR scale) in a range from 0 (corresponding to undamaged plant) to 10 (corresponding to destruction of all plants).

Although a value of 8 or less on this scale means that weed species are likely to overcome the effect of the herbicidal compound and eventually reach a maturity state with seed production, a value of 7, due to the competitive influence of crop plants, is considered acceptable control effect on commercial weed plants. In addition, if the NIR scale is greater than zero, usually one to four changes in the Physiological Change Rock (PRR scale) are determined for each weed species, which is also determined by visual inspection of the plant.

In other words, the NIR scale is a measure of the percentage of weed damage, that is, for example, a rating of 9 means 90% of the weed damage, while the characteristics in a range of physiological changes reflect the nature of the damage, such as necrosis, retardation growth, reduced development, and the like. The NIR scale is a more important value since it is a quantitative measure of the damage rate and is thus a major measure of the herbicidal activity of a given compound.

The relative herbicidal activity of compounds A and B.

The relative herbicidal activity of the compounds A and V against various commonly occurring weed species was determined using the methods and methods described above, the results obtained being shown in Tables I to IV below. These tables indicate the repeated tests on A and V (see Ai, A-2 and B-1, B-2) and their effects on weed species, which are indicated by abbreviations, preemergence with an amount of compound corresponding to 0.056 g / m ² and post-emergence with an amount of compound corresponding to 0.028 g / m 2. The potency of these compounds was determined after 13 days and after 22 days, expressed as a numerical scale indicating the degree of plant damage and a characteristic in a range of physiological changes. Tables I and II below show the results of the pre-emergence test obtained after 13 days and 22 days, and Tables III and IV show the results of the post-emergence test obtained after 13 days and 22 days. the full names and Latin names of the individual weed species and abbreviations with the abbreviations in alphabetical order and their meaning in the range of physiological changes are given.

23 >> 09

Table I

The relative herbicidal activity of the compounds A and V at thirteen days after the pre-emergence of these compounds in an amount corresponding to 0.056 g / m 2.

Weed A - 1 NIX Compound A A - 2 PXR NIR WHOA TEAW 9 No, X 8 No, R JMWD 10 No 10 No MSTD 9 No, Y, X 10 No COFE 7 No, R 7 No, X VTLF 3 No, R j R, No MNGY 7 No, К 4 X YNSG 3 No 2 No, R YLFX i o No 9 No, R, H CBGS 9 R, H, No. 10 No JNGS 9 No, X, H 9 No, R, H WOAT 3 X 0 BNGS 9 No, R 8 No, к

Table I (continued)

Weed Compound В В - 1 Б - 2 NIR WHOA NIR WHOA TEAW 5 R, No. 2 No JMWD 0 0 MSTD 7 No, X and No COFE 6 X, H, No. 2 К VTLF 2 No, X 1 No MNGY 2 X 0 YNSG 0 0 YLFX 8 No, X H, No, X GBGS 9 X, H 9 X, No. JNGS л, H 7 X, X, No. WOAT 7 H, X 1 X BNGS 7 H, X 5 K, K, No.

23> э09

Table II

The relative herbicidal activity of the compounds A and E at twenty-two days after the pre-emergence 2 application of these compounds in an amount corresponding to 0.0> 6 g / m 2.

Weed A - 1 NIK Compound A PRK A - 2 NIK PKR TEAW 8 No, R 8 No лад 8 No, Y, R 10 No MSTD 10 No 10 No COFE 6 No, R 7 No, R VTLF 5 R 6 К MNGY 7 No, R 3 No, R YNGS 1 Cl 1 Cl YLFX 10 No 9 No, H, R CBGS 8 R, No. 9 E, К JNGS 9 H, R 9 No, H, R WOAT 0 1 H BNGS 10 No 8 H, No.

Table II (continued)

Weed В - 1 NIK Compound В PKR В - 2 NIK PRK TEAW 0 0 JMWD 0 0 MSTD 0 0 COFE 2 No 3 No, Η, H VTLF 0 0 Mfe 0 0 YNSG 0 0 YLFX 6 H, R 1 л CBGS ⁸ R 9 R, No. JNGS 4 No, H 4 No, H WOAT 5 H, h 1 N BNGS j No 0

23j509

T III

The potent herbicidal activity of A β E compounds thirteen days after the post-emergence application of these compounds in ^an amount corresponding to 0.028 g / m ²

Weed A - 1 NIK Compound A. PKK A - 2 NIK PRK TEAW 8 No, Z, K 8 No, Z, K 10 No 10 No MSTD 10 No 1 0 No COFE 10 No 10 No VTLF 1 0 No 10 No MNOY 9 No 10 No YNSG 0 0. YLFX 8 H, 'No, R 7 No, Η, K WOAT 5 R, No. 3 R, H BNGS · 9 . No, R 8 No, R, H COTN 7 No, N 7 No, R

Table III (continued) Weed B - 1 NIK Compound B PRK B - 2 NIK WHOA TEaW 6 No, K, Z 6 No, Z, K ЛМВ 9 No, Y, R 8 No, Z, R MSTD 8 No, Z, G 8 No, Z, R COFE 8 No, Z, R 8 No, Z, R VTLF 1 0 No 8 No, Z, R MNGY 6 No, K, Z 5 No, R, Z YNSG 0 0 YLFX 3 No 3 H, No. «ΌΑΤ 3 H 0 BNGS 7 No, h Ď No, R COTN 1 No, R 6 No, R

Т а Ь u 1 к β IV

The relative herbicidal activity of the compounds A and E at twenty-two days after the post-emergence application of these compounds in an amount corresponding to 0.028 g / m ² .

Weed A - 1 NIR Compound A WHOA A - 2 NIR WHOA TEAW 8 No, R, Z 8 No, R, Z JMWD 10 No 10 No MSTD 10 No 10 No COFE 9 No, R, Z 10 No VTLF 10 No 10 No MNGY 9 No, K, Z 10 No YNSG 0 0 YLFX 6 No, H, R 6 No WOAT 3 No 0 BNGS 8 No, R 7 No COTN 6 No, R 5 No, R

Table IV (continued) Weed Compound В В - 1 В - 2 NIR WHOA NIR 'PRR TEAW 4 R, No. 4 No, R, Z JMWD 9 No, К 8 No ESTD 7 No, R, Z - 7 No, R COFE 7 No, R, Z 6 No, R, Z VTLF 10 No 8 No, R, Z MNGY 6 No, R, Z 3 * e, Z YNSG 0 0 YLFX 4 No 3 No WOAT 2 R, No. 1 No BNGS 6 R, No, Cl 5 No, R COTN 4 No, R 3 No, R

Explanatory notes:

Designation of weed species

Abbreviation Latin scientific name Common name BNGS Echinochlca crusgelli hedgehog corns the leg CBGS Digitaria sen rosička krevavá COFE Daubentonia punicea (cav.) D.C. chicory COTN Gossypiuo hirsuuuo cotton (Delta Pine ó JMWD Detura otromcniuo durman obecný JNGS Sorghum halepense Halep sorghum (from seed) MNGY Ip ^^^^ ea purpurea Koth povijnice vysoká MSTD Bra ^ica keber (D.C.) mustard deaf TEAW Sida spinosa VTLF Abn ^ tlm tUeophureti dutHm WOAT Avena fetua oat deaf YLFX Setaria glauce yellow tails YNGS Cyperus esculentus šáchor

Range of physiological changes (designation): Cl = chlorosis

E = limited emergence

H = hormone efficacy of the 2,4-D type

No = necrosis

R = slowed growth

Y = germination delay

Z = recurrence rate

Evaluation of compounds:

NIR = number scale indicating plant damage PRK = range of physiological changes.

Claims (4)

1. Hersiccdnn means that they are touched. Heericidally effective amounts of at least one compound of the formula I are active O O Y in which means And J 'bromo nibo nirossuupOnu, Y 'is hydrogen or Boom haoognn, R is an alkylene group or an alkylene group mcrnoubiOitucvaná cisahující 1 to 3 carbon atoms wherein said substituents are alkyl, Okos ^^ i or Uýdroэςsalkylová cisahující group from 1 to 4 carbon atoms, • ^{R 1} is hydrogen ^to θl ^{yl CV} stapina c ¹ sahuj ^I C ^{I 1 and 10 of} eTOM Uhl ^^ čyklcal ^{í á} ylcv Sapina containing EŽ Θ 3 carbon atoms, an agronomically acceptable ion, phenyl, monosubstituted, disubstituted or trisubstituted phenyl wherein said substituents are selected from the group consisting of halogen, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group or a trifluoromethyl group. 2. The herbicidal composition of claim 1, wherein the active ingredient is a compound of formula (I): And nitro, Ϊ is a chlorine atom, К is an ethylene group, and x? is an alkyl group containing 1 to 10 carbon atoms or a cycloalkyl group containing> 7 carbon atoms. 3. The herbicidal composition of claim 1, wherein the active ingredient is 1- (ethoxycarbonyl) ethyl 4- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate. 4. The herbicidal composition of claim 1, wherein the active ingredient is 1- (ethoxycarbonyl) ethyl 4- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoate.