CH653678A5 - HETEROCYCLIC ESTERS OF PHENOXYBENZOESIC ACID, HERBICIDE COMPOSITION THEREOF AND METHOD FOR CONTROLLING WEEDS. - Google Patents

Description

The present invention relates to heterocyclic esters of phenoxyacetic acid which bear substituents in the two benzene rings. Surprisingly, these new esters have herbicidal activity.

The present invention further relates to herbicidal compositions which contain these heterocyclic esters of phenoxybenzoic acid and furthermore to a process for controlling weeds using these new heterocyclic esters of phenoxybenzoic acid.

The present invention relates to heterocyclic esters of phenoxyacetic acid, which have the following formula I.

(CH2) n

(I)

in which n represents the integer 1 or 2, preferably in the presence of an acid acceptor, for example a tertiary amine.

The reaction between an acid chloride of formula II and the alcohol of formula III can be carried out by bringing together equimolar amounts of the acid chloride and the alcohol in an inert reaction medium, for example in toluene. An excess of the molar amount of an acid acceptor is preferably used in order to ensure that the hydrochloric acid released in the reaction is removed from the reaction mixture. The reaction is typically carried out by letting it react and stir at room temperature. Once the reaction is complete, the desired product can be obtained by first removing the salt of the acid acceptor and then evaporating off the solvent used as the reaction medium. The product obtained in this way can either be used as it is, or it can be further purified in accordance with customary working procedures.

Acid chlorides of the formula II which are suitable for the preparation of the compounds according to the invention can easily be prepared by reacting the corresponding acids with thionyl chloride.

Typical examples of acids that can be used to prepare the acid chlorides of formula II are the following acids:

the 2-nitro-5 - (2-chloro-4-trifluoromethylphenoxy) benzoic acid.

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the 2-nitro-5 - (2,4-dichlorophenoxy) benzoic acid, the 2-nitro-5 - (2-nitro-4-chlorophenoxy) benzoic acid, the 2-nitro-5 - (2-cyano-4-trifluoromethylphenoxy) -benzoic acid,

2-nitro-5 - (4-trifluoromethylphenoxy) benzoic acid, 2-methylthio-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid,

2-chloro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid,

2-bromo-5 - (2-chloro-4-trifluoromethylphenoxy) benzoic acid,

2-ethylthio-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid,

2-propylthio-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid,

the 2-cyano-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid and like acids.

Typical examples of alcohols of the formula III which can be used to prepare the esters according to the invention are the following:

3-hydroxytetrahydrofuran, 3-hydroxytetrahydropyran,

the 4-hydroxytetrahydropyran and similar hydroxytetrahydrofurans or hydroxytetrahydropyrans.

Those compounds according to the invention in which the tetrahydrofuran group or the tetrahydropyran group is bonded to the carboxylic acid group in the 2-position of the tetrahydrofuran radical or tetrahydropyran radical are preferably prepared by mixing the acid corresponding to the acid chloride of the formula II with dihydrofuran or 3,4 -Dihydropyran converts. This reaction can be carried out by bringing the acid and the dihydro-furan or dihydropyran together at room temperature in the presence of a catalytic amount of p-toluenesulfonic acid. In this reaction, the use of an excess of pyran or furan is preferred. Once the reaction is complete, the mixture can be washed and the excess of the starting material evaporated to give the desired product.

The present invention further provides a herbicidal composition which is characterized in that it contains a compound of the formula I as active ingredient.

The present invention further relates to a weed control method, which is characterized in that the weeds or the location where these weeds grow are treated with a toxic amount of the compound of the formula I.

The preparation of compounds according to the invention is explained in more detail using the following examples:

example 1

Preparation of 2-nitro-5- (2-chloro-4-trifluoromethylphen-oxy jbenzoyl chloride

80 g of the 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid and 80 ml of toluene were placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser. Then 80 ml of thionyl chloride were slowly added at room temperature with stirring. Once the addition was complete, the mixture was heated to reflux and stirring continued for an hour. The mixture was then stirred overnight at room temperature. After this time the toluene was evaporated from the reaction mixture and the desired product was obtained in the form of an oil.

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Example 2

Preparation of the 3-tetrahydrofuryl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid

1.76 g (0.02 mole) of 3-hydroxytetrahydrofuran, 50 ml of toluene and 2.0 g (0.02 mole) of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 7.60 g (0.02 mol) of 2-nitro-5- (2-chloro-4-tri-fluoromethylphenoxy) benzoyl chloride in 10 ml of toluene was slowly added with stirring. After the addition was complete, stirring was continued overnight. After this time, the reaction mixture was washed with water and then dried over anhydrous sodium sulfate. The solvent was then evaporated from the dried solution under reduced pressure, leaving a brown oil. This oil was purified by silica gel chromatography, using toluene and mixtures of ethyl acetate plus toluene as the eluent. The purified oil was triturated with ethanol to give the desired product, namely the 3-tetrahydrofuryl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid, in the form of a white solid which had a melting point of 55 ° C. owned.

Example 3

Preparation of the 3-tetrahydrofury ester of 2-nitro-5- (2-bro-mo-4-trifluoromethylphenoxy) benzoic acid

0.04 mole of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 mole of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel.

A solution of 0.04 moles of 2-nitro-5- (2-bromo-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene was slowly added at room temperature with stirring. Once the addition was complete, stirring was continued for about 8 hours. After this time, the reaction mixture was washed with water and then dried over anhydrous magnesium sulfate. The solvent was then evaporated from the dried solution under reduced pressure, leaving a residue. This residue was purified by silica gel chromatography using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product was obtained, namely the 3-tetrahydrofurylester of 2-nitro-5- (2-bromo-4-trifluoromethylphenoxy) benzoic acid.

Example 4

Preparation of the 3-tetrahydrofury ester of 2-nitro-5- (2-nitro-5-trissuormethylphenoxy) benzoic acid

0.04 mole of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 mole of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 moles of 2-nitro-6- (2-nitro-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene was slowly added at room temperature with stirring. Once the addition was complete, stirring was continued for about 8 hours. After this time, the reaction mixture was washed with water and then dried over anhydrous magnesium sulfate. The solvent was then evaporated from the dried solution under reduced pressure, leaving a residue. This residue was purified using silica gel chromatography, using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product was obtained, namely the 3-tetrahydrofuryl ester of 2-nitro-5- (2-nitro-4-trifluoromethylphenoxy) benzoic acid.

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Example 5

Preparation of the 3-tetrahydrofury ester of 2-nitro-5- (2-cy-ano-4-trifluoromethylphenoxy) benzoic acid

0.04 moles of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 moles of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 moles of 2-nitro-5- (2-cyano-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Once the addition is complete, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated off from the dried solution under reduced pressure. This leaves a backlog. This residue is purified using silica gel chromatography using toluene and mixtures of ethyl acetate plus toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuryl ester of 2-nitro-5- (2-cyano-4-trifluoromethylphenoxy) benzoic acid.

Example 6

Preparation of the 3-tetrahydrofury ester of 2-methylthio-5- (4-trissuormethylphenoxy) benzoic acid

0.04 moles of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 moles of triethylamine are placed in a glass reaction vessel which is equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 mol of 2-methylthio-5- (4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Once the entire amount has been added, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated from the dried solution under reduced pressure, leaving a residue. This residue is purified using silica gel chromatography, using toluene and mixtures of ethyl acetate plus toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuryl ester of 2-methylthio-5- (4-trifluoromethylphenoxy) benzoic acid.

Example 7

Preparation of the 3-tetrahydrofury ester of 2-chloro-5- (2-bromo-4-trifluoromethylphenoxy) benzoic acid

0.04 mole of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 mole of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 mol of 2-chloro-5- (2-bromo-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Once the entire amount has been added, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated from the dried solution under reduced pressure, leaving a residue. This residue is purified by means of silica gel chromatography, using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuran ester of 2-chloro-5- (2-bromo-4-trifluoromethylphen-oxy) benzoic acid.

Example 8

Preparation of the 3-tetrahydrofury ester of 2-bromo-5-

10th

(2-chloro-4-trifluoromethylphenoxy) benzoic acid

0.04 mole of 2-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 mole of triethylamine were placed in a glass reaction vessel which is equipped with a mechanical stirrer 5 and an addition funnel. A solution of 0.04 moles of 2-bromo-5- (2-chloro-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Once the entire amount has been added, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated from the dried solution under reduced pressure, leaving a residue. This residue is purified by silica gel chromatography using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuran ester of 2-bromo-5- (2-chloro-4-trifluoromethylphen-20 oxy) benzoic acid.

Example 9

Preparation of the 3-tetrahydrofuryl ester of 2-cyano-5- (2,4-dichlorophenoxy) benzoic acid 25 0.04 moles of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 moles of triethylamine were placed in a glass reaction vessel, which is equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 mol of cyano-5- (2,4-dichlorophenoxy) benzoyl-chloro-30 rid in 20 ml of toluene is slowly added at room temperature with stirring. After the addition is complete, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The solvent is then evaporated off from the dried solution under reduced pressure, a residue remaining. This residue is purified by means of silica gel chromatography, using toluene and mixtures of ethyl acetate plus toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuryl ester of 2-cyano-5- (2,4-dichlorophenoxy) benzoic acid.

Example 10

45 Preparation of the 3-tetrahydrofury ester of 2-À thylthio-5- (2-chloro-4-bromophenoxv) benzoic acid

0.04 moles of 3-hydroxytetrahydrofuran, 50 ml of toluene and 0.04 moles of triethylamine are placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel and a solution of 0.04 moles of 2 Ethylthio-5- (2-chloro-4-bromophenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. After the addition is complete, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated from the dried solution under reduced pressure, leaving a residue. This residue is purified by means of silica gel chromatography, using toluene and mixtures of ethyl acetate plus toluene as the eluent. The desired product is obtained, namely the 3-tetrahydrofuryl ester of 2-ethylthio-5- (2-chloro-4-bromophenoxy) benzoic acid.

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Example 11

Preparation of the 3-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxyi benzoic acid

0.04 moles of 3-hydroxytetrahydropyran, 50 ml of toluene and 0.04 moles of triethylamine are placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 moles of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Once the entire amount has been added, continue stirring for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is evaporated off from the dried solution under reduced pressure, leaving a residue. This residue is purified by means of silica gel chromatography using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product is obtained, namely the 3-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid.

Example 12

Preparation of the 4-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid

0.04 mole of 4-hydroxytetrahydropyran, 50 ml of toluene and 0.04 mole of triethylamine were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 mol of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added with stirring at room temperature. Once the entire amount has been added, stirring is continued for about 8 hours. After this time, the reaction mixture is washed with water and then dried over anhydrous magnesium sulfate. The solvent is then evaporated from the dried solution under reduced pressure, leaving a residue. This residue is purified by means of silica gel chromatography using toluene and mixtures of ethyl acetate and toluene as the eluent. The desired product is obtained, namely the 4-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid.

Example 13

Preparation of the 3-tetrahydropyranyl ester of 2- (methyl-thio-5 (2-chloro-4-trifluoromethylphenoxy) benzoic acid

0.04 moles of 3-hydroxytetrahydropyran, 50 ml of toluene and 0.04 moles of triethylamine are placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. A solution of 0.04 mol of 2- (methylthio-5- (2-chloro-4-trifluoromethylphenoxy) benzoyl chloride in 20 ml of toluene is slowly added at room temperature with stirring. Stirring is continued as soon as the entire amount has been added for about 8 hours after which time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate, and the solvent is evaporated from the dried solution under reduced pressure to leave a residue which is purified by silica gel chromatography, eluting with silica gel chromatography Toluene and mixtures of ethyl acetate and toluene were used as the eluent to give the desired product, namely the 3-tetrahydropyranyl ester of 2-methylthio-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid.

Example 14

Preparation of the 2-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid

20 ml of 2.3 dihydropyran 0.05 mole of 2-nitro-5-

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(2-Chloro-4-trifluoromethylphenoxy) benzoic acid and a spatula tip of p-toluenesulfonic acid are placed in a glass reaction vessel equipped with a mechanical stirrer. The mixture is stirred at room temperature 5 until the carboxylic acid grouping, which is determined with the aid of infrared spectroscopy, can no longer be determined in the reaction mixture. After this time the mixture is dissolved in methylene chloride, washed with a dilute aqueous sodium carbonate solution and dried over water-free magnesium sulfate. The solvent and excess dihydropyran are then evaporated from the dried solution under reduced pressure to give the desired product, namely the 2-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoro-15 methylphenoxy) - benzoic acid.

Example 15

Preparation of the 2-tetrahydrofury ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid 20 0.03 moles of dihydrofuran, 0.025 mole of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid, 25 ml of methylene chloride and a spatula tip of p-toluenesulfonic acids are placed in a glass reaction vessel equipped with a magnetic stirrer. The reaction mixture is stirred at room temperature until the carboxylic acid grouping can no longer be determined in the reaction mixture using the infrared spectrum. After this time, the reaction mixture is washed with dilute aqueous sodium carbonate and then with water. The ge-30 washed solution is dried and the solvent and the unreacted starting material are evaporated off, giving the desired product, namely the 2-tetrahydrofuryl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy ) benzoic acid.

For practical use as herbicides, the compounds according to the invention are generally used as an active ingredient in herbicidal compositions which contain an inert carrier material and a herbicidally effective amount of a compound of the formula I. Such herbicidal compositions, which can also be called herbicidal compositions or herbicidal formulations, enable the active compound to be applied in a desired amount in a convenient manner at the location where weeds occur. The herbicidal compositions can be formulated in solid form, for example as dusts, as granules or as wettable powders, or they can also be formulated in liquid form, for example as solutions, as aerosols or as emulsifiable concentrates.

Dusts can be produced, for example, by grinding 50 and mixing the active compound with a solid inert carrier material, for example talc, clay types, materials containing silicon dioxide, for example silicas, pyrophyllites and the like.

Granulated or granular formulations can be prepared by impregnating granular or granulated carrier materials, such as, for example, the attapulgite or the vermiculite, with the active ingredient, which is usually dissolved in a suitable solvent. The granulated carrier materials generally have particle sizes in the range from about 0.3 to 1.5 mm.

Wettable powders, which can be dispersed in water or in oil until any desired concentration of active compound is reached, can be produced by incorporating wetting agents into concentrated dust compositions.

In some cases, the active compounds are sufficiently soluble in common organic solvents, such as kerosene or xylene, so that they can be used directly as

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Solutions in these solvents can be used. Frequently, solutions of the herbicides can be dispersed in the form of aerosols under a pressure which is higher than atmospheric pressure. However, the preferred liquid herbicidal compositions are emulsifiable concentrates which contain an active compound according to the invention and, as an inert carrier, a solvent or an emulsifier. Such emulsifiable concentrates can be diluted with water and / or with oil to achieve any desired concentration of the active compound, where they are then suitable for application as sprays where weeds are present. The emulsifiers most commonly used in these concentrates are non-ionic emulsifiers or mixtures of non-ionic surfactants with anionic surfactants. With the use of some emulsifier systems, an inverse emulsion, namely a water in oil emulsion, can be prepared which is suitable for direct application at the location where weeds are present.

A typical herbicidal composition according to the invention is illustrated by the following example, in which all amounts are given in the form of parts by weight, unless expressly stated otherwise.

Example 16

Production of a dust

10 parts by weight of the product according to Example 2 and 90 parts by weight of powdered talc were used as starting material.

These components are mixed in a mechanical grinding mixer and grinding is carried out until a homogeneous free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application at the location where weeds are found.

The compounds according to the invention can be applied as herbicides in any manner which is known in this field. One method of combating weeds is to bring the location of these weeds into contact with a herbicidal composition which comprises an inert carrier and, as an essential active ingredient, a compound according to the invention in an amount which is greater than that of the weeds in question herbicidal toxic. The concentration of the new compounds according to the invention in the herbicidal compositions varies very greatly with the type of formulation and with the intended use for which this compound is intended. In general, however, herbicidal compositions will contain from about 0.05% to about 95% by weight of the active compounds according to the invention. According to a preferred embodiment of the invention, the herbicidal compositions contain from about 5% to about 75% by weight of the active compound. The herbicidal compositions may also contain other ingredients, such as pesticides, for example insecticides or nematocides (anti-worms), fungicides and similar ingredients, and they may also contain additives such as stabilizers, spreading agents, deactivators, adhesion-promoting agents, anchoring agents, Contain fertilizers, activators, synergistic substances and the like.

The compounds according to the invention are also useful when they are combined with other herbicidal agents and / or defoliants, drying agents, growth inhibitors and similar other active ingredients in the

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herbicidal compositions described above can be combined. Such other ingredients can make up from about 5% to about 95% by weight of the active ingredients in the herbicidal compositions. Through the use of combinations of these other herbicidal active substances and / or defoliants and / or desiccants and similar materials with the compounds according to the invention, herbicidal compositions can be made available which are more effective in combating weeds and which often give such results, which are not attainable if separate compositions of the individual herbicides are used. Other herbicides, defoliants, drying agents and plant growth inhibitors which can be used in combination with the 1S compounds according to the invention in herbicidal compositions for weed control are, for example, chlorophenoxy herbicides, such as e.g.

2,4-D, 2,4,5-T, MCPA, MCPB, 4 (2,4-DB), 2,4-DEB, 4-CPB, 4-CPP, 2,4,5-TB, 2 , 4,5-TES, 3,4-DA, Silvex and similar 20 such herbicides, carbamate herbicides, such as IPC,

CIPC, Swep, Barban, BCPC, CEPC, CPPC and similar herbicides, thiocarbamate and dithiocarbamate herbicides, e.g. DCEC, methane sodium, EPTX, dialallate, PEBC, perbu lat, vernolate and similar herbicides, substituted urea-2s herbicides, e.g. Norea, Siduron, dichloral-urea, chloroxuron, cycluron, fenuron, monuron, monuron-TCA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and similar herbicides, symmetrical triazine herbicides, such as, for example, simazine, chlorazine, atraon, Des -3o metryn, norazin, ipazin, prometryn, atrazine, trietazin, Si-meton, prometon, propazin, ametryn and similar chloroacetamide herbicides, such as a-Chloro-N, N-dimethylacetamide, CDEA, CDAA, a-chloro-N-isopropylacetamide, 2-chloro-N-isopropyl-acetanilide, 4- (chloroacetyl) morpholine, l- (chloro-35 acetyl) piperidine and the like, herbicides based on chlorinated aliphatic acids, such as, for example, TCA, dala-pon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like, herbicides based on chlorinated benzene acid and chlorinated phenyl acetic acid, such as Example 2,3,6-TBA, 2,3,5,6-TBA, 40 dicamba, tricamba, amiben, fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy-3,4,6-trichlorophenylacetic acid, 2,4-di-chloro-3-nitrobenzoic acid and the like, and also such compounds as aminotriazole, maleic acid hydrazides, 45 phenyl-mercuric acetate, endothal, biuret, technical Chlordan, Dimethyl-2,3,5,6-tetrachloro-terephthalate, Diquat, Er-bon, DNC, DNBP, dichlorobile, DPA, Diphenamid, Dipro-palin, Trifluoralin, Solan, Dicryl, Merphos, DMPA, DSMA, MSMA, Potassium azide, acrolein, benefin, bensulide, AMS, so Bromacil, 2- (3,4-dichlorophenyl) -4-methyl-l, 2,4-oxadiazo-lidin, 3,5-dione, bromoxynil, cacodylic acid, DMA, DPMF, cypromid, DCB, DCPA, dichlon, diphenantril , DMTT, DNAP, EBEP, EXD, HCA, Ioxynil, IPX, Isocyil, Kaliumcy-anat, MAA, MAMA, MCPES, MCPP, MH, Molinat, NPA, 55 OCH, Paraquat, PCP, Picloram, DPA, PCA, Pyrichlor, Se-sone, Terbacil, Terbutol, TCBA, Brominil, CP-50144, H-176-1, H-732, M-2091, Planavin, sodium tetraborate, calcium cyanamide, DEF, ethyl xantogen disulfide, Sindon, Sin-don B, Propanil and the like.

Such herbicides can also be used in the process according to the invention for combating weeds and in the compositions according to the invention for combating weeds in the form of their salts, esters, amides or other derivatives, wherever such derivatives of the respective basic compounds can be used.

Weeds are undesirable plants that grow where you do not want them and have no economic value, and the cultivation of crops

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Growth of ornamental plants or the growth of forage, without the useful plants or the cattle being hindered by medium-sized plants for animals. There will be a large number.

known on weeds, such as annual weeds. The new compounds according to the invention are particularly

which include the following: valuable for combating weeds because they

At • , . Compared to many weed species and groups of weeds, Amaranthus retroflexus (the English name sf., ...,. ... .ff.., ...,,. ~ .. c ,,, ° have a toxic effect, while they are relatively non-toxic toxic to «pigweed»), white goose foot (Chenopodium album),. , ..., n £ n • j ta- „i, c \. c-, rv • • r, are many useful plants. The exact amount of Foxtail, Fingergrass (Digitarla sanguinalis), wild,. j j. . ... . . j ..., °. , r ,,,, c c A, ..., ,, 5; D ■ „■ The required form depends on a variety of fak-sent, field parsley (Thlatis arvense), ryegrass, panicle. r, ° .... . • TI * i • gras (Poa annua), a weed with the English designation Î0 ™ abund, these include, for example, the stubborn chickweed, which is a weed, a Miere or> o k of the respective weed that are controlled should, the starwort, or a hornwort, wild oats, velvet leaf (with weather conditions, the type of soil, the methodology of the English name Velvet leaf), a weed with the suspension che type of useful plants, which are in the same, D n, , ■, c,. Area and related factors. While an English name Purslane, millet (Echino-. ~ 0,,., ,, _ TT \ ji chloor crus galli), a weed with the English term of only 283 g to 56.6 g (1- 2 ounces)

c, e! ,, ".... , °. , s, s active connection per 4 047 square meters (per acre)

nungSmartweed, bird knotweed (Dolygonum aviculare), 15. ,,. , ^ n, .. c -,

f. , r *,, f .. d, •, -c, can be sufficient to achieve a good control, burdock, or hog burdock, wild buckwheat (Fagopyrum),. ,. n f ,,? T. t e ±. j- • tI,. .., n ■, 'TI if there is a slight infestation of weeds, which is a weed with the English name Kochia, a weed. .. ^. e, rt. r> • t. ii growing under unfavorable conditions, a herb with the English name Medie corn cockle,. ° ^ r, (1A J \ AU Ambrosia fR ^ weedì s; niHktel fWh, K nlprarpno wei ^ p carrying amount of 4.5 kg (10 pounds) or even larger Ambrosia (Ragweed), Saudistel (Sonchus oleraceus) white amounts of active Compound per 4 047 square feet of Wegwarte (Cichorium mtybus), croton, a weed with the 20, ^ ^ e English name Cuphea, Teufelszwirn (Cuscuta), Er- (Pro Acre) required if a good control

, e, / Ir cc- ■ v \ \ r ii i wc -1 a strong Belali of difficult to fight multi-tooth

smoke (Fumaria olncianhs), ragwort (Senecio vul- TI, ... .., •..,.. .. .. ^ D,. J

garis), hemp nettle (Galeopsis, e.g. Galeopsis tetrahit, einjäh- ^ 1 (; JJnkraUtem n ° Üg 1St'dl6 UntCr 811118118611 Bedm8un8en riger ball (Scleranthus annuus), milkweed, field pearls

(Spergula), a weed with the English name 25 The herbicidal toxicity of the new invention

Emex, Oryza sativa (jungle rice), pondweed (Potamogeton), compounds can be determined using many recognized test methods.

stinking dog chamomile (Anthemis cotula), Axonopus comfahren shown in the literature,

pressus (carpetweed), purple winch (Ipomea purpurea), rennet such as for testing herbicidal activity in herb (galium), telegraph plant (converting clover) (desmo preliminary process (before infestation) or testing herbicidal

dium gyrans), duckweed (Lemna) and Naias (Naiad). 30 ziden activity in the follow-up procedure (after the occurrence

The weeds to be controlled also include two of the weeds).

year-old weeds and as an example of this are mentioned: the herbicidal activity of the compounds according to the invention

Wild carrot (Daucus carota), a weed with which to fertilize, was illustrated with the help of experiments that use the term matricaria, wild barley (Hordeum vul- pre-treatment to combat a large number of gare), carnation, chamomile, burdock (Arctium lappa ), 35 royal weeds were used. In these experiments, candle (Verbascum thapsus), poplar (Malva rotundi-fo- small plant pots for the greenhouse with dry soil lia), common thistle (Cirsium lanceolatum), dog's tongue were filled and they were seeded with various weed seeds.

(Cynoglossum officinale), moth cottonweed (Verbascum men. 24 hours after or less after introducing the Blattaria) and purple star thistle (Cirsium). Weed seeds were sprayed with water until the

The weeds to be controlled also include 40 soil which was moist and the compounds to be tested were weeds of several years, and as an example of this are the aqueous emulsions of acetone solutions, the emulsifiers.

mentioned: contained, formulated and these were specified in the

Weeds with the English name White Cockle, concentrations sprayed onto the surface of the earth,

perennial rye grass, grasshopper. Aleppo millet (wild negro- After spraying the containers with the soil in millet), sorghum halepense), Canadian thistle (Canada 45 the greenhouse was given and additional

thistle), hedge winch (Convolvulus sepium), dog tooth grass warming applied if necessary and there was a

(Cyonodon daetylon), a type of dock (Rumex acetosella), watering the pots daily or even more often. The frizzy dock (Rumex crispus), Cyperus rotundus (nut plants were grown under these conditions during 15 to 21

grass), a chickweed, or a Miere, or Sternmiere with days and at this point the

the English name field checkweed, dandelion 50, the plants and the extent of the damage was

(Taraxacum officinales), bellflower (Campanula), a posed.

Winch family (Convulvus) with the English name The assessment of the damage to the plants was made after

Field bindweed, a knapweed (Centaurea) performed with the narrow- a grading scale that ranged from 0-10, whereby the term Russian knapweed, gram grass (Boute- the individual marks mean the following:

loua), or Buffalo grass (Buchloë) with the English name- 55

mesquite, flax (Linaria vulgaris), yarrow (Achil- 0 is no damage,

lea), aster, a weed with the English designation 1 or 2 is equal slight damage,

Gromwell (Gruinum milium or Lithospermum officinale), 3 or 4 is even damage,

Horsetail (Eqisetium), North American verbena 5 or 6 is equally severe to severe damage,

(Veronia noveboracensis), a weed with the English strain 60 7, 8 or 9 is equally serious damage

Drawing Sesbania, pond rush (Scirpus lacustris), or ame- 10 is the same as plant death,

rican fluff (Juncus effusus), cattail, Liesch-NE is not an infestation.

piston, pond flask (Typha) and winter cress (cressa).

In the same way, such weeds can be classified as broad. The effectiveness of these compounds is classified on the basis of the leafy weeds or as grassy weeds.

will. From an economic point of view, it is Wünbelle I specified. If numbers with de-

it is worth noting that the growth of such weeds occurs in a controlled manner, this means that in this case the

653 678

8th

results are given, which were obtained from the formation of the mean value of black millet, sorghum halepense from two or more values, from one

OKGS

=

Quickgrass or multiple repetitions of the trials.

WOAT

=

Wild Oat = wild oat = Avenua

In Tables I and II the following abbreviations

5CBGS

fatue tongues used:

=

Crabgrass = fingergrass =

Digitaria sanguinalis

WMSD

= Wild mustard = wild mustard

SPGT

=

Sprangletop = Leptochloa dubia

Brassica kaber

CTGS

=

Cheatgrass = rye biscuit

BDWD

= Bindweed = winch = convulvus

(bromus secalinus)

arvensis

10 SUBT

- -

Sugarbeet = sugar beet = beta

PIGS

= Pigweed = Amaranthus retroflexus

vulgaris

JMWD

= Jimsonweed = Thorn Apple = Datura

COTN

=

Cotton = Cotton = Gossypium

stramonium

SPP-

VTLF

= Velvetleaf = velvet leaf = abutilon

SOYB

=

Soybean = Soybean = Glycine max

theophrasti

15 PTBN

=

Pintobean = speckled bean =

MNGY

= Morning glory = purple winds =

Phaseolus vulgaris

Ipomea purpurea

ALFA

=

Alfalfa = shark grass = Medicago sativa

YLFX

= Yellow Foxtail = yellow Foxtail

SORG

=

Sorgum = millet = Sorghum bicolor

(Setaria lutescens)

WHT

=

Wheat = wheat = Triticum aestivum

BNGS

= Barnyardgrass = millet =

20 RICE

=

Rice = rice = Oryza sativa

Echinochloor crus galli

CORN

=

Com = maize = zea mays

JNGS

= Johnsongrass = Aleppo millet, wild

OAT

=

Oat = oat = Avena spp.

Tested connection

Product of

Example 2

Tested connection

Product of

Example 2

Amount in ounces per acre

1.0

0.5

0.25

0.125

Amount in ounces per acre

1.0 0.5 0.25 0.125

Table I

Preliminary testing and assessment on the 14th and 21st days of the test

WMSD BDWD PIGW

JMWD VTLF

1

MNGY YLFX

BNGS

14

21st

14

21st

14

12

14

21st

14

21st

14

21st

14

21st

14

10th

10th

9

9

10th

10th

NE

NE

10th

10th

10th

10th

10th

10th

10th

10th

10th

7

8th

10th

10th

NE

NE

10th

10th

10th

10th

10th

10th

9

10th

10th

8th

10th

10th

10th

NE

NE

NE

NE

9

9

10th

10th

10th

10th

10th

0

0

9

9

NE

NE

0

0

6

0

7

2nd

8th

g e

t e

s t

e t

e

P

f

1

at

e.g.

21st

10 10 10

3rd

JNGS

OKGS

WOAT

CBGS

SPGT

CTGS

SUBT

SOYB

14 21

14

21st

14

21st

14

21st

14

21st

14

21st

14

21st

14 21

10 10

10th

10th

3rd

5

NE

NE

10th

10th

5

5

10th

10th

9 7

10 10

10th

5

4th

1

9

NE

9

10th

0

0

10th

10th

7 4

5 10

0

0

0

0

10th

10th

9

10th

0

0

10th

10th

3 2

0 2

0

0

0

0

8th

7

5

0

0

0

9

10th

0 0

Tested compound ounces per acre

Product of

Example 2

1.0 0.5 0.25 0.125

COTN

PTBN

ALFA

WHT

RICE

SORG

CORN

OAT

14

21st

14

21st

14

21st

14

21st

14

21st

14

21st

14

21st

14

21st

9

9

10th

10th

10th

10th

6

2nd

10th

10th

10th

10th

5

1

1

3rd

6

5

10th

10th

10th

10th

3rd

0

10th

10th

10th

10th

5

2nd

1

1

0

0

0

0

8th

5

0

0

10th

10th

6

7

3rd

0

0

0

0

0

0

0

3rd

0

0

0

4th

0

1

1

0

0

0

0

In Table II below, the herbicidal activity of compounds according to the invention was determined using the post-processing method, i.e. the compounds in question were used to control a variety of weeds after the weeds appeared, and it was also tested to what extent crops are damaged under these conditions.

In these experiments, the compounds to be tested were formulated as aqueous emulsions, in the specified

60 doses were sprayed onto the leaves of various weed species, which had reached the prescribed size, and also onto the leaves of various crops. After spraying, the plants were placed in a greenhouse and watered daily or more often. The water was not applied to the leaves of the treated plants. In this case, the extent of the damage was assessed after the 10th to 15th day. Again, a scale from 0 to 10 was used for the assessment.

9

653 678

where the grade scale was identical to the one above by an average of two or more repetitions of the given grade scale. Even if values are tests in this case. The results obtained are in the follow-up with decimal points, then this shows that it is summarized in Table II:

Tables

Testing the compound according to Example 2 in the wake method Damage to the plants with an application amount of ounces per acre

Tested

Plant species

1

0.5

0.25

0.125

WMSD

10th

10th

10th

10th

BDWD

10th

10th

10th

10th

PIGW

10th

10th

10th

10th

JMWD

10th

10th

10th

10th

VTLF

10th

10th

10th

10th

MNGY

10th

10th

10th

10th

YLFX

10th

10th

10th

3rd

BNGS

10th

10th

10th

10th

JNGS

10th

10th

10th

10th

QKGS

10th

10th

9

3rd

WOAT

10th

10th

5

2nd

CBGS

10th

10th

10th

10th

SPGT

10th

10th

10th

10th

CTGS

8th

2nd

1

0

SUBT

10th

10th

10th

10th

COTN

10th

10th

10th

10th

SOYB

10th

7

6

4th

PTBN

10th

5

7

6

ALFA

10th

10th

10th

10th

SORG

10th

10th

9

4th

WHT

10th

10th

1

1

RICE

5

1

0

0

CORN

1

5

9

0

OAT

10th

10th

2nd

0

C.

Claims (11)

653 678 2nd PATENT CLAIMS 1. Compound of Formula I / \ vy / \ (8.H2> n (I) in which X is a halogen atom or the trifhiormethyl radical, Y represents a hydrogen atom, a halogen atom, a nitro group or a cyano group, R represents a nitro group, an alkylthio group, a halogen atom or a cyano group and n represents the integer 1 or 2. 2. Compound according to claim 1, characterized in that it is the 3-tetrahydrofuryl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid. 3. A compound according to claim 1, characterized in that it is the 3-tetrahydrofuryl ester of 2-nitro-5- (2-bromo-4-trifluoromethylphenoxy) benzoic acid. 4. A compound according to claim 1, characterized in that it is the 3-tetrahydrofuryl ester of 2-nitro-5- (2-nitro-4-trifluoromethylphenoxy) benzoic acid. 5. A compound according to claim 1, characterized in that it is the 3-tetrahydrofuryl ester of 2-nitro-5- (2-cyano-4-trifluoromethylphenoxy) benzoic acid. 6. A compound according to claim 1, characterized in that it is the 3-tetrahydrofuryl ester of 2-methyl-thio-5- (4-trifluoromethylphenoxy) benzoic acid. 7. A compound according to claim 1, characterized in that it is the 2-tetrahydropyranyl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid. 8. A compound according to claim 1, characterized in that it is the 2-tetrahydrofuryl ester of 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) benzoic acid. 9. Herbicidal composition, characterized in that it contains a compound of formula I as active ingredient. 10. A method of combating weeds, characterized in that the weeds or the place where these weeds grow are treated with a toxic amount of the compound of the formula I. have in which X is a halogen atom or a trifluoromethyl group, Y represents a hydrogen atom, a halogen atom, a nitro group or a cyano group, 5 R has the meaning of a nitro group, an alkylthio group, a halogen atom or a cyano group and n represents the integer 1 or 2. Preferred compounds of the formula 101 according to the invention are those in which X is a chlorine atom, bromine atom or the trifluoromethyl group, Y is the meaning of a hydrogen atom, a chlorine atom, bromine atom, a nitro group or a cyano ! 5 group and R represents a nitro group, a methylthio group, a chlorine atom, a bromine atom or a cyano group. The compounds according to the invention can be prepared by using a reactive acid derivative, preferably an acid chloride of the formula II Cl 25th (II) 30 in which X, Y and R have the same meaning as in formula I, with an alcohol of formula III 35 40 H0- I. (CH2) n (III)