CH643808A5 - SUBSTITUTED DIPHENYL ETHER AND HERBICIDES CONTAINING IT. - Google Patents

Description

The invention relates to certain herbicidally active substituted diphenyl ethers, their use for

Weed control and herbicides containing them. The diphenyl ethers according to the invention have the formula wonn

A halogen, the cyan or nitro group,

X is hydrogen or halogen,

Y is hydrogen, halogen, the cyan, trifluoromethyl or nitro group or an alkyl radical having 1 to 4 carbon atoms, Z is oxygen or sulfur,

R alkylene or monosubstituted alkylene with 1 to 3 C atoms, the substituents being alkyl, oxoalkyl or hydroxyalkyl with 1 to 4 C atoms,

R1 is hydrogen or alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, an agronomically acceptable ion, phenyl or mono-, di- or trisubstituted phenyl, where the substituents are halogen, alkyl or alkoxy having 1 to 10 carbon atoms -Atoms, or the cyan, nitro or trifluoro-

are methyl group,

mean.

Examples of halogen are fluorine, chlorine, bromine and iodine, 60 with bromine or chlorine being preferred. Examples of alkyl and cycloalkyl radicals are methyl, ethyl, isobutyl, n-butyl, t-butyl, n-amyl, heptyl, octyl, iso-octyl, nonyl, decyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. Suitable alkoxy, oxoalkyl and hydroxyalkyl 65 radicals are, for example, methoxy, ethoxy, butoxy, octoxy, oxoethyl, oxopropyl, oxobutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and the like. Methylene, ethylene or propylene are examples of suitable ones

Alkylene residues. Agronomically acceptable ions are alkali metals, such as sodium, potassium or lithium, alkaline earth metals, such as barium or calcium, and ammonium or alkyl or alkanolammonium with up to 4 carbon atoms.

Preferred compounds are those in which Z is oxygen, A is the nitro group, R1 is an alkyl radical having up to 4 carbon atoms, X is hydrogen and Y is halogen.

The compounds of the above formula have herbicidal activity. Specific and preferred examples of such compounds are r- (ethoxycarbonyi) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (Ethoxycarbonyl-methyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoate; 2, carboxyethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 2 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; (Ethoxycarbonyl) methyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; r-ethoxycarbonyl-2-oxopropyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) butyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (phenoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; r- (ethoxycarbonyl) propyl 5- (2-chloro-4-tri-fluoromethylphenoxy) -2-nitrobenzoate; 1'-ethoxycarbonyl-3'-methylbutyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoate; 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoate; 1 '- (Ethoxycarbonyl) -2'-hydroxypropyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoate; 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-cyanobenzoate; 1 '- (Ethoxycarbonyl) ethyl 5- (2,6, dichloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (Ethoxycarbonyl) ethyl 5- (2-chloro-6-bromo-4-trifluoromethylphenoxy) -2-cyanobenzoate; and r- (thioethylcarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate.

It goes without saying that stereoisomers and optical isomers of all the compounds mentioned also belong to the invention.

The compounds according to the invention can be prepared, for example, by reacting a suitably substituted benzoyl halide with an alcohol or a suitably substituted alpha-hydroxycarboxylic acid ester or by reacting a correspondingly substituted benzoic acid with a correspondingly substituted alpha-halocarboxylic acid ester in a manner known per se. The benzoyl halides or benzoic acids and the alpha-halogen or hydroxycarboxylic acids are commercial products or are easy to produce. In particular, an at least stoichiometric amount of an appropriately substituted benzoyl halide is added with stirring to an appropriately substituted alpha-hydroxycarboxylic acid, preferably in the presence of an acid acceptor such as triethylamine, pyridine, N, N-dimethylaniline or the like. Since the reaction is exothermic, the benzoyl halide is added in portions such that the temperature of the reaction mixture does not rise significantly above 15 ° C. If the compounds according to the invention are prepared by reacting a substituted benzoic acid with an alpha-halocarboxylic acid ester, the latter is preferably used in the presence of an azo compound such as 1,5-diazobicyclo- (5.4.0.) - undec-5-ene for the former (DBU) given. An inert solvent, such as benzene, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran or the like, can be used in both synthetic methods, if desired. When the addition of the corresponding reactants has ended, the reaction mixture is heated under reflux until the reaction has reached the desired level of completeness. The reaction mixture is then cooled to room temperature and washed successively with dilute acid, dilute base and water, after which the phases are separated. The sub3 643 808

Substituted diphenyl ethers are then separated from the organic phase in a known manner, such as by evaporation, crystallization, vacuum drying and the like. If desired, the product obtained can be purified, for example by recrystallization. The following Examples 1 to 12 show synthetic possibilities for compounds according to the invention.

example 1

io 1 '- (Ethoxycarbonyl) ethyl-5- (2-chloro-4-trifluoro-

methylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 1.18 g (0.01 mol) of ethyl lactate and 0.79 g (0.01 mol) of i5 pyridine in 30 ml Load benzene. 3.79 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 20 ml of benzene are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 6 20 hours. The cooled reaction mixture is washed in a separating funnel in succession with 30 ml portions of n-hydrochloric acid, water, n-sodium hydroxide solution and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 2.89 g of the title compound are obtained as a pale yellow oil. NMR (acetone, d6) 7.3-8.35 (complex multiplet, 6H);

5.35S (quartet, H);

4.28S (quartet, 2H); 30 1,625 (doublet, 3H);

1,255 (triplet, 3H).

Example 2

r- (Ethoxycarbonylmethyl) ethyl 5- (2-chloro-4-trifluoro-35 methylphenoxy) -2-nitrobenzoate

A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is charged with 1.32 g (0.01 mol) of ethyl 3-hydroxybutyrate and 1.1 g (0.01 mol) of triethylamine in 30 ml of benzene. 3.69 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 20 ml of benzene are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 6 hours. The cooled reaction mixture is washed successively in a separating funnel with 30 ml portions of n-hydrochloric acid, water, n-sodium hydroxide solution and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 3.75 g of the title compound are obtained as a brown oil. NMR (acetone d6) 7.2-8.35 (complex multiplet, 6H);

5.55 (quartet, 1H);

4,155 (quartet, 2H);

2,755 (doublet, 2H); 55 1.35 (doublet overlapping triplet,

6H).

Example 3

2'-carboxyethyl 5- (2-chloro-4-trifluoro-60 methylphenoxy) -2-nitrobenzoate

A three-necked flask of 250 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is loaded with 2.70 g (0.03 mol) of 3-hydroxypropionic acid and 2.38 g (0.03 mol) of pyridine in 110 ml of methylene chloride . 11.37 g (0.03 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 30 ml of methylene chloride are added dropwise to the stirred solution at about 20 ° C. Heat is generated completed access

643 808

the reaction mixture is refluxed for 22 hours. The cooled reaction mixture is washed successively in a separating funnel twice with 100 ml portions of n-hydrochloric acid and once with 100 ml water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 11.8 g of the title compound are obtained as a viscous yellow oil.

NMR (acetone d6) 7.2-8.4S (complex multiplet, 6H);

4.35 (triplet, 2H);

2,675 (triplet, 2H).

Example 4

2 '(Ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 20 ml of ethanol and 5 ml of pyridine in 30 Load ml of methylene chloride. 2.26 g (0.005 mol) of 2 '- (chlorocarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate in 15 ml are added dropwise to the stirred solution at about 20 ° C. Given methylene chloride. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 42.5 hours. The reaction mixture is concentrated in a rotary evaporator at 55 ° C. The concentrated residue is taken up in 100 ml of methylene chloride and washed successively in a separating funnel with portions of 30 ml of n-hydrochloric acid, water, 7% strength aqueous ammonia and again water. The organic phase is dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 1.3 g of the title compound are obtained as yellow 01.

NMR (chloroform) 7.0-8.15 (multiple, 6H);

4.35 (multiple, 4H);

2,655 (triplet, 2H);

1.35 (triplet, 3H).

Example 5

(Ethoxycarbonyl) methyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 1.25 g (0.012 mol) of ethyl glycolate and 0 , 80 g (0.01 mol) pyridine in 35 ml methylene chloride. 3.79 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 20 ml of methylene chloride are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 42.5 hours. The cooled reaction mixture is washed in a separating funnel in succession with 30 ml portions of n-hydrochloric acid, water, 7% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55.degree. 3.5 g of the title compound are obtained as a yellow oil.

NMR (chloroform) 7.0-8.45 (Multiple, 6H);

4,825 (singlet, 2H);

4,255 (quartet, 2H);

1,315 (triplet, 3H).

Example 6

r-Ethoxycarbonyl-2'-oxopropyl-5- (2-chloro-4-tri-fluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 3.61 g (0.05 01 mol) 5- (2-chloro-4-trifluoromethylphen-

4th

oxy) -2-nitrobenzoic acid and 1.53 g (0.01 mol) 1,5-diazabi-cyclo- (5.4.0.) - undec-5-ene (DBU) in 50 ml benzene. 1.65 g (0.01 mol) of ethyl 2-chloroacetoacetate are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 20.5 hours. The cooled reaction mixture is washed successively in a separatory funnel with 30 ml portions of n-hydrochloric acid, water, 7% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55.degree. 3.1 g of the title compound are obtained as a brown oil.

NMR (acetone, d6) 7.2-8.25 (multiple, 6H); i5 5.85 (singlet, 1H);

4.25 (quartet, 2H);

2.35 (single, 3H).

Example 7

20 1 '- (Ethoxycarbonyl) butyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 3.61 g (0.05 01 mol) 5- (2-chloro-4-trifluoromethylphen-25 oxy) -2-nitrobenzoic acid and 1.53 g (0.01 mol) DBU in 50 ml benzene. 2.19 g (0.01 mol) of ethyl 2-bromo-valerate are added dropwise to the stirred solution at about 20 ° C. After the addition has ended, the reaction mixture is heated under reflux for 22 hours. 30 The cooled reaction mixture is washed successively in a separating funnel with 30 ml portions of n-hydrochloric acid, water, 7% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 2.2 g of the title compound are obtained as a brown oil.

NMR (acetone d6) 7.2-8.25 (Multiple, 6H);

5,255 (triplet, 1H);

4,285 (quartet, 2H); 40 0.8-1.95 (multiple, 10H).

Example 8

r- (Phenoxycarbonyl) methyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate 45 A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 3.61 g (0.01 Mol) of 5- (2-chloro-4-trifluoromethylphenyloxy) -2-nitrobenzoic acid and 1.53 g (0.01 mol) of DBU in 50 ml of benzene. 2.29 g (0.01 mol) of phenyl-2-bromoacetate are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 22.5 hours. The cooled reaction mixture is washed in a separating funnel in succession with 30 ml portions of n-hydrochloric acid, water, n-sodium hydroxide solution and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55.degree. 2.58 g of the title compound are obtained as a greenish syrup. 60 NMR (acetone, d6) 7.0-8.255 (Multiple, 11H);

5.55 (quartet, 1H);

1,685 (doublet, 3H).

Example 9

65 1 '- (Ethoxycarbonyl) propyI-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer

is loaded with 3.61 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoic acid and 1.53 g (0.01 mol) of DBU in 35 ml of benzene. 1.95 g (0.01 mol) of ethyl 2-bromo-butyrate in 15 ml of benzene are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 24 hours. The cooled reaction mixture is successively in a separatory funnel with 30 ml portions of n-hydrochloric acid, water,

Washed 7% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55.degree. 1.2 g of the title compound are obtained as a brownish syrup.

NMR (acetone, d6) 7.2-8.25 (multiplet, 6H);

5,155 (triplet, H);

4.25 (quartet, 2H);

1.95 (quartet, 2H);

0.8-1.35 (overlapping triplet,

6H).

Example 10

r-Ethoxycarbonyl-3'-methylbutyl-5- (2-chloro-4-tri-fluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 1.60 g (0, Load 01 mol) of ethyl a-hydroxyisocaproate and 0.79 g (0.01 mol) of pyridine in 40 ml of methylene chloride. 3.79 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 10 ml of methylene chloride are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 46.5 hours. The cooled reaction mixture is washed successively in a separating funnel with 25 ml portions of n-hydrochloric acid, water, 3.5% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated at 55 ° C. in a rotary evaporator. 3.99 g of the title compound are obtained as a viscous brown oil. NMR (acetone, d6) 7.2-8.35 (multiplet, 6H);

5.25 (triplet, 1H);

4.25 (quartet, 2H);

1.85 (multiplet, 3H);

0.8-1.45 (multiplet, 9H).

Example 11

r-ethoxycarbonyl-2'-hydroxypropyl-5- (2-chloro-4-tri-

fluoromethylphenoxy) -2-nitrobenzoate A three-necked flask of 500 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 19.56 g (0.04 mol) of l'-ethoxycarbonyl-2'-oxopropyl-5- (2- chlorine-4-trifluoromethylphenoxy) -2-nitrobenzoate (prepared according to Example 6) and 100 ml of methanol. 3.14 g (0.05 mol) of sodium cyanoborohydride and a few drops of methyl orange indicator are added to the stirred solution at about 20 ° C. A solution of 2N hydrochloric acid in 75:25 vol / vol methanol is added dropwise in such a way that the indicator remains colored. The reaction mixture is refluxed for 20 hours, then cooled and concentrated in a rotary evaporator at 55 ° C. The concentrated residue is taken up in 200 ml of diethyl ether and washed in a separating funnel with portions of 100 ml of n-hydrochloric acid, water, n-sodium hydroxide solution and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator. 18.1 g of the title compound are obtained as a yellow syrup.

5,643,808

NMR (acetone, d6) 7.2-8.35 (multiplet, 6H);

4.25 (multiplet, 3H);

3.25 (quartet, 2H);

1.35 (doublet overlapping triplet, s 5H).

Example 12

1 '- (Ethoxycarbonyl) ethyl-5- (2-chloro-4-tri fluoromethylphenoxy) -2-bromobenzoate io A three-necked flask of 100 ml with a dropping funnel, a reflux condenser and a magnetic stirrer is mixed with 1.18 g (0 , 01 mol) of ethyl lactate and 0.79 g (0.01 mol) of pyridine in 50 ml of methylene chloride. 2.07 g (0.005 i5 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoyl chloride in 10 ml of methylene chloride are added dropwise to the stirred solution at about 20 ° C. This generates heat. After the addition has ended, the reaction mixture is heated under reflux for 66 hours. The cooled reaction mixture is washed in a separating funnel 20 successively with 30 ml portions of n-hydrochloric acid, water, 7% aqueous ammonia and again water. The organic phase is separated off, dried over sodium sulfate and evaporated in a rotary evaporator at 55 ° C. 2.2 g of the title compound are obtained as 25 yellow syrupy liquid.

NMR (acetone, d6) 7.0-8.05 (multiplet, 6H);

5,258 (quartet, 1H);

4,185 (doublet, 3H);

1,685 (doublet, 3H); so 1,185 (triplet, 6H).

Although some of the compounds according to the invention are explained in more detail by the above Examples 1-12, it goes without saying that any compound within the scope of the present invention can be produced by the methods described, only the starting materials having to be changed.

The compounds of the invention have been found to regulate the growth of a variety of undesirable plants, such as weeds, when applied to a planting area in an amount effective as a herbicide before or after weed emergence. A “herbicidally effective amount” is understood to be an amount which is sufficient to damage weeds in such a way that they can no longer recover. The amount of a particular compound or a mixture of several compounds to achieve this effect can vary within wide limits and depends on various factors, such as the resistance of a particular weed, the density of the weed population, the climatic conditions, the Soil nature, the type of application and the like. Small amounts such as one or less kg / ha (0.2 pound / acre) up to more than 10 kg / ha (10 pound / acre) may be required, depending on the circumstances. The effectiveness of a particular compound against a particular weed can be determined in the usual way by laboratory or field tests.

The compounds of the invention can be used as such or together with agronomically acceptable excipients, inert carriers, other herbicides and conventional compounds such as pesticides, stabilizers, fertilizers and the like. The compounds according to the invention can be applied in a known manner as such or with substances other than dusts, granules, wettable powders, solutions, suspensions, aerosols, emulsions, dispersions and the like. If they are mixed with other agents commonly used in agriculture, their share can vary widely

643 808

ken, for example from about 0.05 to about 95% of the total weight of the mixture. The proportion of the compounds according to the invention in such mixtures is normally from about 5 to about 75% by weight.

The compounds according to the invention can be used to control a large number of broad-leaf and grass weeds, it being possible to apply amounts of about 2 kg / ha (2 pounds / acre) or less before or after emergence, without crop plants, such as corn, wheat, Rice and soybeans are damaged. Examples of weeds that can be controlled effectively are wild mustard (Brassica kaber); yellow foxtail (Setaria glauca); Blood millet (Digitaria sanguinalis); Coffee weed (Sesbania spp.); Velvet leaf (Abutilon theophrasti); Aleppo millet (sorghum halepense); Barn grass (Echinochloa crusgalli); Jimson weed (Datura stramonium); Tea weed (Sida spinosa); Tali morningglory (Roth); and the same.

Some of the compounds prepared according to Examples 1 to 12 were tested against certain weeds under precise laboratory conditions (lighting, temperature, moisture) for herbicidal activity. Of the 5 selected weeds, seeds were planted in flat bowls. For pre-emergence tests, the trays were treated immediately after sowing. For post-emergence tests, the dishes were treated with the selected compound after a two-week germination period. The application was carried out io by spraying a solution of the connection. Then the growth level was observed and the toxic effect was determined periodically.

The following table shows the weeds examined and the selected compounds (numbering according to 15, Examples 1 to 12). In each case, the corresponding compound was applied in an amount corresponding to approximately 2 kg / ha before emergence.

Table I

II

IV

V

VI

VII

VIII

IX

Sida spinosa

X

X

X

X

Datura stramonium

X

X

X

X

X

X

X

X

X

Brassica kaber

X

X

X

X

X

X

X

X

Setaria glauca

X

X

X

X

X

X

X

X

Digitaria sanguinalis

X

X

X

X

X

X

X

X

Sorghum halepense

X

X

X

X

X

X

X

Sesbania spp.

X

X

X

X

X

Abutilon theophrasti

X

X

X

X

X

Tali morningglory

X

X

X

X

X

Avena fatua

X

X

X

Echinochloa crusgalli

X

X

X

X

X

X

The X show the tests carried out. The following table shows the tests carried out afterwards. It was found that the weeds within 21 to running tests, which were carried out with amounts as above, were either killed or killed and those which were about 2 kg / correspond to ha.

were curably damaged.

Table!!

I II III IV V VI VII VIII IX X

Sida spino & a

X

X

X

X

Datura stramonium

X

X

X

X

X

X

X

X

X

Brassica kaber

X

X

X

X

X

X

X

X

X

X

Setaria glauca

X

X

X

X

X

X

X

Digitaria sanguinalis

X

Sorghum halepense

X

X

X

X

Sesbania spp.

X

X

X

X

X

X

X

X

X

X

Abutilon theophrasti

X

X

X

X

X

X

Tali morningglory

X

X

X

X

X

X

X

X

X

Avena fatua

X

X

X

X

Echinochloa crusgalli

X

X

X

Xanthium strumarium

X

X

X

X

The X again show the tests carried out. In post-emergence application compared to pre-emergence application of each of these tests, it was found that the weeds possess, if they are used in amounts below 5 kg / ha, in particular

within 21 to 22 days after application, especially in amounts of about 2 kg / ha or less,

were neither killed nor incurably damaged. 60 det. Compounds in which A is the nitro group have

It has been found that compounds according to the invention have approximately the same activity both in pre-emergence and in genes in which the substituent A is not the nitro group, and also in post-emergence application, if they are used in amounts but, for example, halogen, in particular bromine (see about 2 kg / ha or less applies.

Example 12), a somewhat better herbicidal activity

Claims (8)

643 808 PATENT CLAIMS 1. Compounds of the formula Î -R1 r-7 bliss A halogen, the cyan or nitro group, X is hydrogen or halogen, Y is hydrogen, halogen, the cyan, trifluoromethyl or nitro group or an alkyl radical having 1 to 4 carbon atoms, Z oxygen or sulfur, R alkylene or monosubstituted alkylene with 1 to 3 C atoms, the substituents being alkyl, oxoalkyl or hydroxyalkyl with 1 to 4 C atoms, R1 is hydrogen or alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, an agronomically acceptable ion, phenyl or mono-, di- or trisubstituted phenyl, where the substituents are halogen, alkyl or alkoxy having 1 to 10 carbon atoms, or the cyan, nitro or trifluoromethyl group, mean. 2. Compounds according to claim 1, characterized in that Z is oxygen. 3. Compounds according to claim 1, characterized in that R1 is an alkyl group with up to 4 carbon atoms. 4. Compounds according to claim 1, characterized in that A represents the nitro group. 5. Compounds according to claim 1, characterized in that A is halogen or the cyano group. 6. Compounds according to claim 1, characterized in that A is the nitro group, Z is oxygen, R1 is one 15 Alkyl radical with up to 4 carbon atoms, X is hydrogen and Y is halogen. 7. Compounds according to claim 1, from the group 1 '- (ethoxycarbonyl) ethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonylmethyl) ethyl-5- (2-chloro 4-trifluoromethylphenoxy) -2-nitrobenzoate; 2'-carboxyethyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 2 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethylphen- 20 oxy) -2-nitrobenzoate; (Ethoxycarbonyl) methyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1'-ethoxycarbonyl-2'-oxopropyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoate; 1 '- (ethoxycarbonyl) butyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (phenoxycarbonyl) ethyl-25 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1 '- (Ethoxycarbonyl) propyl 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1'-ethoxycarbonyl-3'-methylbutyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; 1'-eth-oxycarbonyl-2'-hydroxypropyl-5- (2-chloro-4-trifluoromethyl-30 phenoxy) -2-nitrobenzoate; r- (Ethoxycarbonyl) ethyI-5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoate. 8. Herbicidal agent, characterized in that it contains an effective amount of one or more compounds according to claim 1. 35 9. A method of controlling weeds, characterized in that a planting area is treated with an effective amount of one or more compounds according to claim 1 before or after weeds emerge.