DD218543A5 - HERBICIDAL AGENT - Google Patents

Abstract

The invention relates to a herbicidal composition containing as active ingredient a novel Aryloxybenzoesäureverbindung the general formula I and can be used as a selective herbicide in wheat and soybean cultures. A herbicidally active compound is prepared, for example, by reacting the potassium salt of 5- (3-hydroxyphenyl) tetrazole with 3,4-dichloro (trifluoro) benzene to give 5- (3- (2-chloro-4-trifluoromethylphenoxy) -phenyl) tetrazole becomes.

Description

Herbicidal agent

 5 Field of application of the invention:

The invention relates to a herbicidal composition which contains as active ingredient an aryloxybenzoic acid compound having a tetrazole group and is used in agriculture.

Characteristic of the known technical solutions:

Known are the 2-nitro-5- [2'-chloro-4 '- (trifluoromethyl) phenoxy! Benzoic acid, also called acifluorfen, and their salts and their use as herbicides, especially for weed control in soybean cultures.

Numerous derivatives of acifluorfen have also become known, in particular alkyl, cycloalkyl, thioalkyl and phenyl esters and also monoalkylamides or dialkylamides.

Such compounds are disclosed in U.S. Patents 3,652,645; 3,784,635; 3,873,302; 3,983,168; 3,907,866; 3,798,276;

3,928,416, 4,063,929. 2 5

Object of the invention:

The aim of the invention is to provide a novel herbicidal composition which is an excellent herbicidal

, '' '' - ./2. '

- ^{:. :} -.:- ^:. ' ^: "-" L · .--. - 2 - ' _ ''. , 'Activity has. _t

Explanation of the essence of the invention:

The herbicidal composition according to the invention contains, in addition to customary excipients and carriers, as the active ingredient a compound corresponding to the general formula (I)

(D

¹ 5 in the: '-' ·.

X represents a haloatoD or a lower alkyl group substituted with one or more halogen atoms,

Y is a hydrogen or halogen atom or one of the groups

CF ₃ , CN, NO ₂ or CH ₃ ,

D represents a nitrogen atom or the group -C (Z) =, in which Z is a hydrogen or halogen atom,

W is a hydrogen or halogen atom or the nitro group,

R represents a hydrogen or halogen atom or an aliphatic or aromatic group, an alkylthio, amine, acyl, alkylsulfonyl or arylsulfonyl or hydroxy or cyano group, these various groups being optionally substituted; Possible substituents which may be mentioned are the following atoms or groups: halogen, alkoxyalkoxy, alkoxy, hydroxy, lower alkyl or acyl, carboxyl, salts and esters (carboxylates) of this carboxyl group, such as, for example, lower alkoxycarbonyl groups. ,

/ 3

In particular, R may have one of the following meanings:

- Optionally substituted alkyl group, for example a lower alkyl group, which is optionally substituted by one or more of the abovementioned atoms or groups; < - aryl group, optionally substituted, for example with; same substituents as the aforementioned;

- lower Alkeny! group;

lower alkynyl group;

lower alkylthio group, optionally substituted, for example with one or more halogen atoms;

- amino group, optionally substituted, for example with one or more lower alkyl groups or with an "acyl group;

-CO-R ¹¹ , in which R ^{1 is} a substituent, for example the group OH or a lower alkoxy group or an aryloxy group or an amino group, which in turn may be substituted; '- SO ₅ -R ", in which R" is a substituent such as a

Ä ''',' ...

Alkyl or aryl group; ²⁰ or a group -OH or -CN.

As used herein, "lower" group means that it contains at most 6 carbon atoms.

The dashed lines indicated in the general formula (I) indicate the presence of tautomerism.

The compounds of the general formula (I) in which R represents a hydrogen atom are acidic and can therefore form agriculturally acceptable salts with suitable bases. These salts can also be used as herbicides and thus also fall within the scope of the invention. Examples of such salts are metal salts, for example alkali salts such as sodium, potassium or lithium salts or alkaline earth salts such as calcium or magnesium salts or ammonium salts or mono- or polysubstituted ammonium salts such as isopropylammonium salts, triethanolammonium salts, morpholiniura salts and the like.

^V '' ... , , V / 4

  , , _ 4 -

Depending on the position of the substituent R on the tetrazole ring, the herbicidally active compounds of the general formula (I) appear in two isomeric forms (IA) and (IB), which also fall within the scope of the invention and in which the various substituents have the same meaning as in the general formula (I):

(IA)

Among the compounds of the general formulas (I), (IA) and (IB), a group which is preferred because of its excellent herbicidal properties consists of the compounds in which:

X is the trifluoromethyl group, Y is a chlorine atom / D is the group -CH =, w is the nitro group and

R represents an alkyl group which is optionally substituted, for example with a lower alkoxycarbonyl group

/ 5

ίο

i * 2 0

The herbicidally-active compounds of the general formula (I) and their agriculturally useful ones are prepared.

Usable salts can be used in various ways

The compounds of the general formula (I) can be prepared by the action of a phenyltetrazole of the general formula (II):

(II)

in which W and R have the same meaning as in the formula (I) and A is an OH group or a halogen atom, preferably a fluorine or chlorine atom, to a compound of the general formula (III) ^x

(HD

In which X, Y and D have the same meaning as in the general formula (I) and B represents a halogen atom, preferably a fluorine or chlorate or the OH group, with the proviso that 3 is selected other than A, i. that B represents a halogen atom when A represents the OH group and 0 that B represents the OH group when A represents a halogen atom.

If it is desired to prepare a compound of the general formula (I) in which W is a hydrogen atom, then it is preferable to use j as the starting compound · phenyltetrazole of the formula (III) in which A represents the OH group,

/ 6 '

, - 6 - .. '. , , ,

and a compound of the formula (III) in which B is a halogen atom.

If a compound of the general formula (I) is to be prepared in which W is the nitro group, the starting compound is preferably a corresponding phenyltetrazole of the formula (II) in which A is a halogen atom and a compound of the formula (III) where B stands for the OH group.

The reaction between the phenyltetrazole of the formula (II) and the compound of the formula (III) is generally carried out in the presence of a basic agent at a temperature in the range from 80 to 180 ^° C., for example in an aprotic polar solvent, for example dimethylsulfoxide, dimethylformamide, Dimethylacetamide, N-methyl-2-pyrrolidone, acetonitrile, acetone or other equivalent aprotic polar solvents. ,

As a basic agent is advantageously used sodium or potassium hydroxide or sodium or potassium carbonate. It is also possible to use the compounds of the formulas (II) or (III) with OH group in the form of a previously formed alkali phenolate.

The phenyltetrazole of the general formula (II) used as starting compound can be prepared by the action of NaN ₃ on a nitrile of the general formula (V)

wherein A and W have the same meaning as in the general formula (II) * with the proviso that when W is the nitro group, A is necessarily one

/ 7

Is halogen. This reaction is carried out according to the method described by K. Kadaba in Synthesis-1973-S, 71-84.

This gives the phenyltetrazole of the general formula (II) in which A and W have the same meaning as before and R is a hydrogen atom.

The phenyltetrazole compounds of general formula (II), for which the substituent is other than a hydrogen atom, can be prepared starting from the previously obtained phenyltetrazole, by the action of a reaction partner of general formula (VIII)

R-T (VIII)

in which R has the same meaning as before and T represents a leaving reactive group, for example a halogen atom, preferably an iodine or bromine atom, or an arylsulfone group such as benzenesulfonyloxy, toluenesulfonyloxy, xylenesulfonyloxy groups.

The compounds of the general formula (I) in which W represents a halogen atom or the nitro group while the other substituents have the same meaning as in the formula (I) can also be prepared by halogenating or nitrating the compound of the general formula (I) be, at the W one. Is hydrogen atom and corresponds to the following formula (IV):

(IV)

in which X, Y, D and R have the same meaning as in the general formula (I).

/ 3

The nitration of the compound of formula (IVI can be carried out using a conventional nitrating agent such as nitric acid or potassium nitrate, preferably in the presence of sulfuric acid, optionally in an inert organic solvent, advantageously a chlorohydrocarbon such as methylene chloride, perchlorethylene, chloroform, etc., generally at low temperature in the Range, from -20 to + 2O ⁰ C is worked.

The halogenation of the compound (IV) can be carried out, for example, by the action of a halogen in a solvent such as acetic acid and by heating, for example, refluxing.

The compounds of the formula (D in which W and R represent a hydrogen atom while the other substituents and symbols have the same meaning as in the formula (I) can also be prepared by the action of NaN on a nitrile of the general formula (VI)

(VI)

in which X, Y and D have the same meaning as in the general formula (I), are prepared according to the method of K. Kadaba described above. This gives the compounds of the general formula (VII)

(VII)

in which the various symbols and substituents have the same meaning: as before,. _f :

Pie compounds of the general formula (I) for which R is a substituent other than a hydrogen atom can also be prepared starting from compounds of the general formula (VII) whose preparation has been described above, by the action of a reaction partner of the general formula ( VIII)

R - T - (VIII)

in which R and T have the meanings given above, to this compound.

This reaction is generally carried out in an inert organic solvent at a temperature in the range of 20 to 15O ° C. ,

As indicated above, the salts of the compounds of general formula (I) wherein R represents a hydrogen atom can be obtained by treating these compounds with a corresponding base, preferably with caustic soda.

After completion of the reaction according to any of the procedures described above, the compound of general formula (I) or the salt of this compound is separated from the reaction mixture by the usual procedures, for example by distilling off the solvent or by recrystallizing the compound from the reaction medium. If necessary, the compound is then purified by conventional means, for example by recrystallization from a suitable solvent or by liquid phase or vapor phase chromatography.

agents never used in the invention generally contain in addition to the active ingredient i. the compound of general formula (I), one or more carriers or diluents which are solid or liquid, as well as being agriculturally acceptable, and one or more

several surfactants that are also agriculturally acceptable. If necessary, they may additionally contain various excipients which are also agriculturally compatible.

, , '; ''. -

In general, the compositions according to the invention contain about 0.05 to 99% by weight of active compound, about 0.01 to 20% by weight of one or more surface-active agents and about 1 to 99.95% by weight of one or more carriers or diluents, liquid or solid. , 'ί

Suitable solid carriers are natural or synthetic silicas such as diatomaceous earth, clays and natural or synthetic silicates such as talc, attapulgite, vermiculite, kaolinites, montmorillonite, calcium silicate and aluminum silicate calcium carbonates, natural or synthetic resins such as polyvinyl chloride and others more in question.

Suitable liquid carriers may be water, alcohols such as isopropanol and glycols, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, etc., ethers, aromatic or araliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum fractions such as kerosene, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and other more

5 turn. , ,

When the carrier is water or a common organic solvent, the agents according to the invention advantageously contain a surface-active agent in addition to the active ingredient

0 means. , "" '

The surfactant may be an emulsifier, a dispersant, a deflocculant or a wetting agent, as well as ionic or nonionic. 5

The surfactant can be advantageously

''. '. '''- 1Ί -. "· '" ^: . '/

Use fatty alcohols or substituted phenols, especially alkylphenols or arylphenols or fatty or fatty amines. It is also advantageous to use esters of fatty acids and sorbitan, sucrose derivatives, alkali metal or alkaline earth metal salts of lignsulfonic acid and alkylaryl sulfonic acids, salts of esters, of sulfosuccinic acid, of alkyl betaines or

Use sulfobetaines, etc.

\. '

Mc Cutcheon's Detergents and Emulsifiers 1975 Annual MC Publ. Ridgewood, New Jersey, USA, describes numerous surfactants and gives recommendations for their use.

U.S. Patent 3,713,804 discloses numerous anionic or cationic or nonionic surfactants useful for agriculture. The surfactant to be used in the compositions of the invention may be readily selected by those skilled in the art from the compounds or linking groups described in the two cited references or elsewhere.

In addition to the active ingredient, carrier and surfactant, the compositions of the invention may contain other adjuvants such as dispersants other than surfactants, peptizers, protective colloids and thickeners, adhesives that improve resistance to rain, stabilizers, preservatives, corrosion inhibitors, dyes, scavengers , Anti-foaming agents, anti-caking agents, antigel agents

30 medium and more.

The agents according to the invention can be provided in very different solid or liquid forms.

y ,  ·.

Examples of solid compositions are powders for dusts, with an active ingredient content of up to 100%, and granules and microgranules, especially those obtained by extrusion, through

Prepressing, by impregnation of a granulated carrier or by granulation are obtained from a powder, wherein the active ingredient content in these granules is 1 to 80% in these latter cases. These solid forms are generally used dry without subsequent dilution. >

Examples of liquid or liquid agents for use are wettable powders or wettable powders, solutions or teasable concentrates, suspension concentrates, solutions, especially the water-soluble concentrates, emulsions and dispersions.

The powders for dusts usually contain. 0.1 to 5% by weight of active ingredient, an inert carrier which may be a vehicle for impregnation, such as a silica, and, if necessary, 0 to 10% by weight of one or more stabilizers and / or other additives such as penetrants , Adhesives, anticaking agents and dyes. They are usually prepared by premixing the active ingredient with the inert carrier and then grinding the mixture in a mill.

The granules and microgranules, which generally contain little active ingredient, can be prefabricated and then impregnated or mass-produced, for example by sputtering or extrusion. In the latter case, binders must be added, as well as border-active agents to ensure rapid disintegration on the soil. They generally contain 0.5 to 10 wt .-% of active ingredient, 0 to 10 wt .-% additives such as stabilizers, release retarders, binders and solvents.

The wettable powders or wettable powders are usually prepared so that they contain 20 to 95% of active ingredient, and in addition to the solid carrier Q to 5% of a wetting agent,

From 3 to 10% of a dispersing agent; and _f if necessary, from 0 to 10% of one or more stabilizers and / or other additives such as penetrating agents, coupling agents or agents for modifying the formation of lumps, dyes, etc.

To prepare these wettable powders or wettable powders, the active ingredient is mixed in suitable mixers with the additional substances and ground in mills or other comminution devices. In this way, sprayable powders are obtained which can advantageously be wetted and brought into suspension. They can be suspended in water at any desired concentration and this suspension is particularly well suited for application to the foliage of the plants.

The solutions or emulsifiable concentrates contain the active ingredient dissolved in a solvent, generally in an aromatic hydrocarbon and additionally, if necessary, an auxiliary or co-solvent which may be a ketone, an ester, an ether, etc.

In general, they contain 5 to 60% by weight per volume of active ingredients, 2 to 20% by weight per volume of an emulsifier and can be prepared, for example, by dissolving the active ingredient in the solvent or mixture of solvent and emulsifiers with good stirring and with heating or cooling become.

Starting from these emulsifiable solutions or concentrates, it is possible by dilution with water to obtain emulsions of any desired concentration which are particularly suitable for the use of the compounds according to the invention.

, '. '/ 14

The suspension concentrates or "flowable" suspensions consist of a suspension of fine solid particles of the active ingredient in water or a non-solvent oil and are prepared so that one obtains a stable flowable product that does not settle, they usually contain 10 to 75 wt. -% active ingredient, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents, 0 to 10% corresponding additives such as anti-fouling agents, corrosion inhibitors, stabilizers, penetrants and adhesives and: as a carrier water or an organic Fluid in which the active ingredient is little or not; is soluble. Certain solid organic substances or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze,

15 medium for the water.,

These suspension concentrates are prepared by very finely ground the active ingredient and then dispersed in the liquid Trä-2Oj ger containing the excipients; Finally, the dispersion obtained is treated in a ball mill. Starting from the suspension concentrates, it is possible to thoroughly thicken with water suspensions of any desired composition.

j Center received. 2 5! , · ·

These aqueous suspensions or emulsions, as described above, for example the agents which are prepared by dispersing a wettable powder, an emulsifiable. Concentrate or a suspension concentrate with water 0, fall within the general scope of the compositions according to the invention.

The agents according to the invention are suitable for the selective weed control in crops, especially in rice and wheat crops. In this case, an effective against the weeds, but not phytotoxic to the crops amount of a compound of the general formula (I) applied before emergence of these crops. The amount of active ingredient may vary depending on the compound used, the type of crop, the climatic conditions and the nature of the weeds to be destroyed. ,

EXAMPLES

The following examples serve to illustrate the invention. The structure of the various compounds was characterized by their IR spectrum, by their NMR spectra, and by elemental analysis. The NMR spectrum was recorded in deuterated chloroform in the presence of tetramethylsilane as standard. The results are shown in Table 1, where "IR" is the absorption band.

indicating in cm.

25 Example 1

Preparation of 5- / 3 '- (2 "-chloro-4" -trifluoromethylphenoxy) -phenyiytetrazole; Compound No. 1.

0 In a 1 1 three-necked flask, 0.15 1 methanol were introduced; then, portionwise, 13.2 g of potassium hydroxide in cookies

/ 16

and then at once 18 g corresponding to 0.1 mol of 5- (3 "-hydroxyphenyl) tetrazole, crystallized with 1 mol EUO t, wherein the temperature was kept below 30 ⁰ C = was held for about half an hour at this Temperature and the solvent was distilled off under reduced absolute pressure of about 1 mbar to give, in the form of a brown oil, the potassium salt of 5- (3'-hydroxyphenyl) tetrazole.

The brown oil was then poured into 100 ml of dimethyl sulfoxide dissolves and the solution 20.5 g (0.1 mol) of 3, -4-DiChIOr- f (trifluoromethyl) benzene was added and the reaction mixture heated WAN rend ^v 5 hours at 130 ⁰ C; then the temperature was allowed to cool to room temperature (about 25 ° C). The reaction _; mixture was then poured into 500 ml of water. The watery |; Phase was extracted with twice 100 ml of ethylene chloride. Then the aqueous phase was isolated and acidified with concentrated hydrochloric acid to pH = 1. The formation of crystals consisting of unreacted tetrazole and an oil dissolved in 200 ml of methylene chloride was observed. The obtained organic phase was washed several times with water and dried over sodium sulfate. The solvent was then distilled off and the resulting oil was stirred with 100 ml of water. The resulting dark crystals were spun off, washed with water and oven dried and finally recrystallized from a 50:50 mixture of water and ethanol. This gave 13.5 g

Compound No. 1 of the formula

Yield: 38% 3 5 m.p. 173 ^° C.

The O-O-hydroxyphenyl) tetrazole used as the starting compound was prepared by the action of NaN 2+ on C 3+ -cyanophenol in dimethylformamide in the presence of ammonium chloride in an analogous manner as described in Synthesis, 1973, pp. 71-84.

Compound No. 1 was also obtained according to the second method described below: To a three-necked flask was added 17.6 g (0.059 mol) of 3- (2'-chloro-4 * -trifluoromethylphenoxy) benzonitrile, 4.2 g (0.065 mol). NaN ₃ , 3.4 g (0.065 mol) of ammonium chloride and 30 ml of dimethylformamide. The reaction mixture was heated at 100 ° C for 4 hours, then allowed to cool to room temperature and poured into 500 ml of water. A solution was obtained, to which 6N hydrochloric acid was added to pH = 1 and stirred for 10 minutes. A white precipitate formed, which was filtered off and then washed with water. After centrifuging and drying in air, 19.5 g of compound no. 1 were obtained.

The 3- (2'-chloro-4'-trifluoromethylphenoxy) benzohitrile had been obtained by the action of trifluoroacetic acid on 3- (2'-chloro-4'-trifluoromethylphenoxy) benzamide.

25 Example 2 .

Preparation of 5- ^ 2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenyl / tetrazole "Compound No. 2,

In 40 ml of concentrated sulfuric acid, 9.2 g (0.027 mol) of compound No.1 were dissolved and added to the solution thus obtained 40 ml of 1,2-dichloroethane ·.

While maintaining the reaction mixture at 0 ^° C. with stirring, 2.7 g (0.027 mol) of potassium nitrate were slowly added over 15 minutes _; added; then the mixture became another

held at this temperature for half an hour and finally at room temperature for one hour.

The resulting mixture was poured into 400 g of a mixture of ice and water. After extracting with twice 100 ml of dichloroethane, the organic phase was dried and then the solvent was distilled off. 8 g (78% of Aufuteute) of an 80:20 mixture of 5- £ 2'Nitro-5 '- (2 "-chloro-4" -trifluorraethylphenoxy) phenyl7tetrazol and 5- / 2'-nitro-3 · - ( 2 "-chloro-4" -trifluörmethy! phenoxy) phenyl / tetrazole.

By chromatography on silica with a mixture of ethanol, CH ₂ Clo and acetic acid in a volume ratio of 1.5 15: 0.1 as EIuens gave 4.2 g of the desired compound no. 2 of the formula

Ν -Ν

O-

Yield 47%. Melting point 142 ° C;

and 0.4 g of 5 ^ - / 2 '-nitro-3' (2 "-chloro-4" -trif luormethylphenoxy) phenyl7tetrazol, -the at 206 ⁰ C melted.

Example 3

Preparation of the sodium salt of Compound No. 2, This salt is Compound No. 3.

In 10 ml of water and one equivalent of 1N sodium hydroxide solution were dissolved 1.16 g of compound no. The water was distilled off in vacuo at 6O ⁰ C to give _p 0 9 g of the desired compound in the form of a gelben.Feststoffes of formula

Cl

Yield 75% melting point above 25O ⁰ C, "

10 Example 4

Preparation of 2-methyl-5- / 2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenyltetrazole, Compound Nr, 4A and 1-Methyl-5 / 2'-nitro-5'- (2 "-chloro-4" -trifluoromethylphenoxy) -phenyl / tetrazo ^ Compound No. 4B,

In a 250 ml three-necked flask were added 7.72 g (0.02 mol) of Compound No. 2, 14.2 g (0.1 mol) of methyl iodide, 5υ ml of dimethylformamide, and 2.76 g (0.02 mol) of anhydrous potassium carbonate submitted and the reaction mixture heated to 70 ⁰ C for 15h. The solvent was then distilled off in partial vacuum (10 mbar) and the remaining mixture taken up with 100 ml of water and twice 100 ml of CH ₃ Cl ₂ . The organic phase was separated and dried over sodium sulfate. After distilling off the solvent in vacuo, 8 g of an oil which was chromatographed on silica with diisopropyl ether as the eluent. Thus, 5.1 g of Compound No. 4A of the formula was obtained

N - N- CH-

Yield 63% _RH 35 Melting point 90-92 ° C; and 0.5 α compound No. 4B of the formula

which melted at 148 ^U C.

According to another preparation process, Compound No. 4A could also be prepared by nitration of 2-methyl-5- / 3 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenyljtetrazole (melting point 8O ⁰ C, yield 72%). ; this latter compound, in turn, was obtained by alkylating Compound No. 1,

15 Example 5

Preparation of 2-methyl-5-p-2 ^l -nitro-5 '- (2 ^II , 4 ^ll -dichlorophenyl) phenyltetrazole Compound No. 5.

In a TOO ml three-necked flask, 5.4 g (0.024 mmol) of 2-methyl-5- (2'-nitro-S'-fluorophenyl) tetrazole, 3.9 g (0.024 mol) of 2,4-dichlorophenol, 3.3 g (0.024 mol) of potassium carbonate and 50 ml of dimethylformamide presented. The reaction mixture was stirred at room temperature for 30 minutes and then heated to 80 ^° C. for 7 hours and then allowed to cool. The solvent was evaporated in vacuo. An oil was obtained which was taken up with 150 ml CH ₂ Cl ₂ ; then was washed three times with 50 ml of H ₂ O uhd the organic phase isolated. After drying the organic phase over sodium sulfate, it was filtered and the solvent was evaporated; This gave a yellow oil which was recrystallized from a mixture of equal volumes of diisopropyl ether and hexane. Filtration, washing with twice 15 ml of diisopropyl ether, centrifuging and air drying yielded 5.8 g

5 desired compound of the formula. >

'- 21 -

N - N - CH ₃

Melting point 115 ^° C., yield 66 _%%

The starting 2-methyl-5- (2'-nitro-5'-fluorophenyl) tetrazole was prepared by alkylating 5- (2-nitro-5-fluorophenyl) tetrazole in acetone with CH-I in the presence of K ₃ CO ₃ received. The 5- (2'-nitro-5-fluorophenyl) tetrazole, in turn, had been obtained by nitrating 5- (3'-fluorophenyl) tetrazole with nitric acid. , ..

Examples 6 to 15;

Following the procedure of Example 4, starting from a corresponding compound, compounds Nos. 6-15 were prepared.

The compounds obtained in the various Examples 1 to 15, with the exception of the compound, No. 4B (each compound has the Nr, the corresponding example) of the formula: y

(X) X- (I)> - Ο-Π)> - w -

The significance of the substituents X, W and R for the various compounds and the yield obtained and the melting point of the compound or its spectral properties are summarized in Table (1). The connections, the

have an asymmetric carbon, come as. Enantiomers R and S before. In this case, the formula (X) as well as the formula (I) is to be adjusted so that it defines both forms or the mixture of the two forms in either equivalent proportions (racemate) or with predominant proportion of one or the other enantiomer,

The following compounds can be prepared by an analogous procedure as in Example 4; 2- (1-Methoxycarbonyl-ethyl) -5 ^ - / 2 '-nitro-5' - (2 "-chloro-4" -trifluoromethyl-phenoxy) -phenyl / tetrazole (Enantiomer R), 2- (1-Methoxycarbonyl- ethyl) -5- / 2 -nitro-5 '- (2 "-chloro-4" -trifluoromethyl-phenoxy) -phenyltetrazole (enantiomer S), 2- (1-methoxycarbonyl-ethyl) -5- / 2' -nitro-5 '- (3 "-chloro-5" -trifluoromethyl-phyridyl-2 "-oxy) phenyl / tetrazole (Raceraat and its enantiomer R and its enantiomer S),

Examples 16-20 below show the herbicidal properties of the compounds according to the invention.

Example 16

5 Herbicidal activity in pre-emergence application in the greenhouse.

An aqueous suspension of the following composition was prepared:

30 - active ingredient 40 mg

- Tween 80. 50 rag

- distilled water containing 1 "* (per mille), with the f-weight, Scurol O ad 40 ml,

'/ 23

in which the active ingredient finely ground and then suspended in the water containing Tween 80 and Scurol 0 _f .

Tween 80 is a surfactant consisting of polyoxyethylene sorbitan monolaurate,

Scurol O is a surfactant consisting of polyoxyethylene alkylpheriols, mainly the Konderisationsprodukt of octylphenol and 10, mol ethylene oxide, 10

The aqueous suspension was then diluted, if necessary, with distilled water containing 1% eScurol O to the desired concentration.

Pots with a diameter of 6.5 cm and height 8, cm were used, half of which contained clay mud and half river sand.

In each pot, 30 seeds of one of the following

20 led plant species designed:

abbreviation

Wheat (Triticura sativura), Variety Caton ...., TRIT Foxtail (Alopecurus rayosuroides). ,,,., ... ALOP Avian (Avena fatua),.,.,.,,,,, AVEN

25 lentils (Lens culinaris), variety

big blonde .. ,,, ..., ....,. LENS Radish (Raphanus sativus), variety rot

pink with white lace,, .., ... RAPH

Forage turnip (Beta vulgaris), variety

0 Ceres., .... BETA

Salad (Lactuca sativa), variety golden yellow ,,., LACT Buckwheat (Polygonura fagopyrum) ,, ..,., ...,. ,, FAG ( Amaranth (Amaranthus caudatus) ..,.,.,, ,, ,,, AMA

The pre-emergence treatment was carried out by spraying the seed kernels with the aqueous active ingredient suspension (spray mixture) in the desired concentration, each pot containing about 0.3 ml of the aqueous suspension.

After treatment, the seed surface was allowed to dry; then the seeds were covered with a < 2 mm thick layer of earth.

Twice a day, the pots were watered by spraying; they were kept in a greenhouse at a temperature of 22 - 24 ° C and at a relative humidity of 70 to 80% under artificial exposure, which corresponded to the level of the plants about 5000 lux, during 16 consecutive hours within 24 h.

Twenty-one days after the treatment, the number and height of the live plants in the drug-treated pots was noted, as well as the number and height of the same plants in control pots treated under the same conditions but without the drug.

In this way, the numerical percentage reduction (extermination) was determined, which was calculated as follows:

Number of live plants in the treated pots

N% =: -. - _____-; --_- χ 100,

Number of live plants in the canisters

and the percent reduction in height (growth) of the plants, which was calculated as follows;

Mean height of living plants in the treated TÖdfen

H% = - _:. ----. -:. 1 χ 100,

Mean height of the living paws in the control pots

/ 2

Based on N% and H%, the percentage was calculated based on the control experiments:

N% χ Η%

³ 100

The numerical values obtained in this way are summarized in Table (2). In this table, the value 0 means complete herbicidal activity and the number 100 means complete absence of herbicidal activity.

Example 17 Herbicides Postemergence treatment in the greenhouse.

The procedure was as in Example 16 with the following modifications:.

After the seeds had been laid, they were covered with a layer of earth about 5 mm thick; the pots were placed in the greenhouse and the seeds were allowed to germinate until the plants were obtained at the desired stage of development;

the treatment with the compounds according to the invention took place when the plants reached the following stage-

2 5 th: '·. '

- 2 to 3 leaf stage in wheat, foxtail, lettuce and amaranthus

- 3 real leaves in lenses

- 2 well-developed cotyledons on buckwheat, turnips

3 0 and

In this post-emergence treatment, the solution or suspension of the active ingredient was sprayed on the plant and then allowed to dry on the plant, ' ^:

As in the previous example, the results were noted 21 days after the treatment and thus the percentage effect on the control experiments in the manner described in the previous example

5 determined.

The numerical values are summarized in Table (3).

Example 18 10

Herbicidal activity and selectivity towards greenhouse crops in postemergence treatment.

The procedure was as described in Example 17

15 using the following plants:

Crops: Rice (Oryza sativa)

Wheat (Triticum vulgare)

Weeds: foxtail (Alenecurus myosuroides) millet (Echinochloa crus-galli)

20 giant foxtail (Setaria viridis)

Indian Mallow (Abutilon theophrasti) Hard Grass (tropical weed) (Sida spinosa) Chrysanthemum (Chrysanthemum annuum) Chamomile (Matricaria raatricarioides)

2 5 honorary ice (Veronica persica)

Plantain (Plantago lanceolata) Amaranth (Amaranthus caudatus)

Blacker Nightshade (Solanum niqrum) Hot Mustard (Sinapis alba)

30 field winch (Convolvulus arvensis)

Vogrelmiere (Stellaria media)

The percentage results based on the control experiments were determined in the same manner as in Example 17. The results are summarized in Table (4).

_ 27 _

Example 19 _Λ

Herbicidal application before emergence of the plants.

In 9 χ 9 χ 9 cm pots, which were filled with light field soil, seeds were designed, the number of which was based on the type of plant and the thickness of the seed.

The pots were treated with a spray mixture in an amount corresponding to a dose of 500 l per ha containing the active ingredient in the desired concentration.

The treatment with the spray mixture thus takes place on the not yet covered with soil seeds - as a spray mixture are generally referred to here all diluted with water means, as applied to the plants or these are treated with them.

The spray mixture used was an aqueous suspension of the active ingredient containing 0.1% by weight of Cemulsol NP 10, a surfactant consisting of polyoxyethylated alkylphenol, mainly polyoxyethylated nonylphenol, and 0.04% by weight of Tween 20, a surfactant 5 Agent consisting of polyoxyethylene sorbitoleate. contained.

This suspension was obtained by mixing and finely grinding the ingredients to an average particle size <40 μΐη. 'ι' 30

Depending on the active ingredient concentration of the spray mixture, the applied active ingredient dose was 0.125 to 2 kg / ha.

ι After the treatment the seeds were coated with an approximately

3 5 3 mm thick layer of earth covered.

The pots were then placed in trays in which they received the necessary water from below and were kept at room temperature below 70% relative humidity for 21 days

held.

After 21 days, the number of live plants was counted in pots treated with the active ingredient-containing spray mixture, as well as the number of live plants in a control pot which had been treated under the same conditions but with a spray mixture without active ingredient. In this way, the percentage of eradication of the treated plants relative to untreated control plants was determined. A percent kill of 100% means that the plant in question has been completely destroyed; a percent kill of 0% indicates that the number of live plants in the pot treated was equal to the number of plants in the control pot. The results of this Example 19 are summarized in Table (5).

2 0 Example 20 Herbicidal application after plant emergence,

In 9 χ 9 χ 9 cm large. Pots. Seeds, which numbered according to the plant species and the thickness of the seed, were laid out, which were filled with light field soil. The seeds were then covered with a layer of soil about 3 mm thick and allowed to germinate until the plantlets reached the desired stage. The treatment stage for the grass weeds was the stage "2nd leaf in formation". The appropriate stage for soy was the "1st unfolded three-leaved leaf" stage. The stage of treatment for the other dicotyledonous plants was the stage "unfolded cotyledons," real leaf in development ".

The pots were then sprayed with the spray mixture containing the active ingredient in the desired concentration / amount corresponding to a feed rate of 500 l / ha.

The spray mixture was prepared in the same manner as in Example 19.

Depending on the active substance concentration of the spray mixture, the amount of active substance or dose applied was 0.125 to 2 kg / ha,...

The treated pots were then held in vats containing the water from below and kept at room temperature below 70% relative humidity for 21 days.

After 21 days, the results were determined as in Example 19. They are summarized in Table 5.

The plants tested in Examples 19 and 20 are listed in Table 6. *

20 '

The compounds of the invention generally have excellent activity over dicotyledonous plants when pre-applied; they are especially effective in postemergence treatment of the main weeds 5 in soybean crops such as American Indian mallow, purple morning glory and Norway burdock.

Example 21 '

Meshable powder -

aJ. · Active ingredient · '50%

30 Sodium Ligi-suifonate ¹ 5.%

Sodium dibutylnaphthalenesulfonate - 1%

Clay (kaolin) 44%

b) / active substance '50%

^; Sodium and / or calcium ligno-sul-

fonat (deflocculant) 5%

Isopropylnaphthalenesulfonate (anionic wetting agent) 1% silica, to prevent lumping 5% kaolin (filler) 39%

- 31 Table 1

Connection X W H 38 Fp ("C) Spectral properties or NMR 1, CP 1 § H H ' · 47 173 2 CF ₃ ^m 2 N / A . 75 142 3 CF ₃ MD ₂ KH ₃ 63 <250 4A ^ 3 NO, 66 92 5 Cl NO ₂ 45 115 i 6 CF ₃ NO ₂ 1-C ₃ H ₇ - 37 67 7 CF ₃ NO ₂ -CH ₂ OOOC ₂ H ₅ 50 oil 8th CF ₃ MD ₂ CHCOOC ₂ H ₅ (R 1) 65 127 9 CF ₃ NO ₂ KXXDC ₂ H ₅ 95 oil NMR 1.25-2.00 4.23-5.68 10 CF ₃ NO 2 -CH ₂ CH ₂ COOC ₂ H ₅ 65 140 11 CF ₃ NO ₂ CH ₃ CHOOOCH ₃ CR ₁ S) 66 132 12 CF ₃ NO ₂ CHCOOCH ₃ (R, S) 71 oil NMR 2.03 - 3.75 5.74 13 CF ₃ * ° 2 L ₂ OOOO ₁₃ 61 oil NMR 0.98 - 2.47 3.78 - "5.53 114 _; ^ 3 r ° 2 J-CH ₂ OCH ₂ CH ₂ OCH ₃ 47 132 J15 zf ₃ Id ₂ I oil IR 1588, 1536, 1327, 1270, 1130, 1082

/ 32

Table 2

Greenhouse herbicidal activity in pre-emergence application, relative to control experiments 100: - Control - no herbicidal activity .0: = full herbicidal activity

Connection no. Dose kg / na 1 TRIT ALOP AVEN LENS RAPH BETA LACT FAG AMA i 1 10 32 36 55 85 100 37 100 60 15 2 1 70 29 75 29 7 3 16 100 0 4A 2.2 34 0 11 35 26 44 0 1 0 6 1 80 14 76 100 90 56 2 60 0 7 1 83 32 66 41 100 100 100 100 0 8th 1 80 63 90 100 5 5 0 75 0 10 100 100 100 46 13 3 13 60 0

Table 3 "

Greenhouse herbicidal activity in postemergence treatment, relative to control experiments 100: "= control - no herbicidal activity 0: = 'full' herbicidal activity

Connection no. Dose kg / ha TRIT ALOP AVEN LENS RAPH BETA LACT FAG 1 10 100 100 100 75 0 57 100 - 2 1 64 56 73 32 0 10 • 0 0 4 A 2.2 39 0 / 22 17 0 0 0 0 6 1 77 10 73 8th 9 3 4 0 7 1 100 34 80 67 25 16 0 6 8th 1 83 75 83 8th 0 0 2 0 10 1 100 88 100 54 6 4 10 1

- 34 -. ·:. ;

Table 4

herbicides Greenhouse activity during postemergence treatment, based to control attempts

1OQ s = control - no herbicidal activity 0 s = full herbicidal activity

Dose kg / ha

Oeyza sativa Triticum vulgaris Alopecurus ayosuroides Echinochloa crus-galli Setar ia vie: id is Abuti lon theophrasti Sida spinoea Chrysanthemum annuujn Matricaria raatr icarioides Veronica persica Plantation lanceolate Acacanthus Caudatus Solanura nigrun Sinapis alba Convolvulus arvensis Stellaria aedia

connection No. 8 No. 3 No. 4A 0.5 0.5 0.5 88 54 8 5 100 61 67 13 4 6 34 15 96 0 47 50 0 20 20 0 15 2 3 8 ι 15 0 0 4 0 0 0 O 8th 0 0 0 3 0 54 7

/ 3 5

Table 5

Connection no. Dose kg / ha preemergence ECH LDL AEU IPO SIN 100 BLE SOJ postemergence BCH LOL ABU IPO SIN ΧΛΝ BLE SOJ 9 2 0.5 0.125 100 20 100 50 100 30 0 50 60 20 95 100 100 100 0 0 11 2 0.5 0.125 80 0 100 30 100 0 0 Ö 30 20 90 100 100 100 0 0 12 2 0.5 0.125 30 0 80 0 80 100 0 0 20 0 80 100 90 30 0 0 13 2 0.5 0.125 0 30 100 50 100 100 0 0 90 30 LOO 100 100 100 0 0 14 2 0.5 0.125 0 20 100 30 100 0 0 0 30 0 LOO 100 100 50 0 0 0 0 100 0 80 100 0 0 20 0 80 100 100 JtJL · _rr o_ _T _ around 100 100 100 LOO 100 50 40 0 100 30 LOO 100 100 XOO 20 30 100 50 100 30 100 0 0 0 100 20 .00 100 100 100 0 0 80 20 100 0 100 50 0 0 90 20 LOO 100 100 100 0 0 80 0 100 30 100 0 0 0 30 0 90 100 100 100 0 50 20 0 50 30 100 0 0 0 30 0 90 100 100 100 0 50 0 0 80 0 90 30 0 0 20 0 30 100 100 100 0 0 100 0 90 70 100 0 0 0 80 0 30 ' 100 100 LOO 0 0 50 0 0 0 100 0 0 0 20 0 20 100 100 LOO 0 Q 0 0 0 0 95 0 0 0 0 0 90 95 LOO 0 0

0 - identical to control 00 = complete eradication of plants

crops: Triticum sativum BLE wheat Glycine max. SOJ soy

weeds:

Chicken millet Echinochlca crus-galli ECH

American Indian mallow Abutilon theophrasti ABU

Spitzklette Xanthium pennsylvanicum XAN

Ackersenf Sinapis arvensis SIN

Purple winds Ipomea purpurea IPO

Raygrass Lolium multi-florum LOL

725534

Claims (6)

invention claim 1, herbicides, g e k e η η ζ ei c h η e t characterized in that it is in addition to conventional excipients and carriers as the active ingredient an aryloxybenzoic acid compound of the general formula,. ,.; (I) contains, in the: X is a halogen atom or a lower alkyl group substituted with one or more halogen atoms, Y represents a hydrogen or halogen atom or one of the groups CF ₃ , CN, NO ₂ or CH ₃ , D is a nitrogen atom or the group -C (Z) * is _f in Z is a hydrogen or halogen atom, W is a hydrogen or halogenator or the nitro group , R represents a hydrogen or halogen atom or an aliphatic or aromatic group, an alkylthio, amino, acyl, alkylsulfonyl or arylsulfonyl, or hydroxy or cyano group {, these various groups are optionally substituted _t or an agriculturally acceptable Salt thereof ^: / 2 2. Composition according to item 1, characterized in that in the given formula (I) of the active ingredient R is a group with one or more halogen atoms) and / or with one or more alkoxy, OH, lower acyl, carboxyl - or carboxylate group (η) is substituted. 3. Means according to item 1 or 2, characterized in that R is a hydrogen or halogenato or a group selected from the following groups: optionally substituted alkyl or aryl group, lower alkenyl or alkynyl group, optionally substituted lower alkylthio group, optionally substituted amino group CO-R ', in which R' is a substituent such as an OH, lower alkyl, aryloxy or amino group, - SO-R '' ι in which R ¹ 'is a substituent such as an alkyl or aryl aryl group, - OH and - CN. 2 0 4. Means according to one of the items 1 to 3, characterized in that X is the trifluoromethyl group, Y is a chlorine atom, D is the group -CH =, W is the nitro group or a hydrogen atom and R is an optionally sub- 25 represents substituted alkyl group. 5. Composition according to one of the items 1 to 4, characterized in that it contains 0.5 to 95 wt .-% of active ingredient 6. Composition according to any one of items 1 to 5, g e k e η η characterized in that it contains 1 to 95% of carrier and 0.1 to 20% surfactant. 7234