NL8402312A - ARYLOXYBENZOIC ACID DERIVATIVES AND USE THEREOF AS HERBICIDES. - Google Patents

Description

i% _ï *

Aryloxybenzoic acid derivatives and their use as herbicides.

This invention concerns new aryloxybenzoic acid derivatives with tetrazole group, the preparation of these new compounds, preparations containing them, and their use as herbicides.

The 2-nitro-5- (21-chloro-41-trifluoromethylphenoxy) benzoic acid (also referred to as "acifluorfen") and its salts are known, as well as their use for controlling weeds between soy plants.

Numerous derivatives of the acifluoro-phen have been proposed, especially alkyl, cycloalkyl, thioalkyl and phenyl esters, as well as monoalkyl and dialkylamides thereof. These compounds are described in U.S. Pat. Nos. 3,652,645, 3,784,635, 3,873,302, 3,983,168, 3,907,866, 3,798,276, 3,928,416, and 4,063,929.

This invention pertains to aryloxybenzoic acid derivatives other than heretofore described, which exhibit excellent herbicidal activity. The compounds according to the invention are characterized in that they are according to formula 1, in which X represents a halogen atom or a lower alkyl group substituted by one or more halogen atoms, Y represents a hydrogen or halogen atom or a group CF ^, CN, NO2 or CH3, D represents a nitrogen atom or the group -C (Z) =, wherein Z is a hydrogen or halogen atom, 25 W represents a hydrogen or halogen atom or a nitro group, R represents a hydrogen or halogen atom or an optional substituted aliphatic, aromatic, alkylthio, amino, acyl, alkylsulfonyl, arylsulfonyl, hydroxy or cyano group, the possible substituents of which are halogen, alkoxy, alkoxyalkoxy, hydroxy, lower alkyl or acyl, carboxyl and salt or ester thereof (e.g. lower alkoxycarbonyl).

8402312 - 2 - S 'f

More particularly, R may have any of the following meanings: optionally substituted alkyl, eg lower alkyl substituted by one or more of the above-mentioned atoms or groups, optionally substituted aryl, eg with any of the above substituents; lower alkenyl, lower alkynyl, lower alkylthio optionally substituted by one or more halogen atoms, amino optionally substituted by one or more lower alkyl groups or by an acyl group, -CO-R 'wherein R' represents a substituent , for example, a hydroxy, lower alkoxy, an aryloxy or an amino group, the latter of which may optionally also be substituted again, -SC ^ -R "wherein R" is a substituent, for example an alkyl or aryl group , or a group -OH or -CN.

By "lower alkyl groups" here are meant groups with up to 6 carbon atoms.

The dotted lines in formula 1 indicate that tautomerism occurs here.

The compounds of formula 1 wherein R is a hydrogen atom are acidic in nature and can thus form salts with appropriate bases, which can also be used as herbicides in the context of the invention. As examples of such salts one can mention those with alkali metals such as sodium, potassium and lithium and with alkaline earth metals such as calcium and magnesium, and salts with ammonium bearing one or more substituents such as isopropylammonium, triethanol ammonium, morpholinium, etc.

Depending on the position of substituent R on the tetrazole ring, the compounds of formula 1 may exist in two isomeric forms, according to formulas 1a and 1b, both of which are included in the invention.

8402312, * * - 3 -

Among the compounds of formulas 1, 1a and 1b, a limited group is preferred in which X is the trifluoromethyl group, Y is a chlorine atom, D is the group -CH =, W is a nitro group, and R is a an optionally substituted alkyl group (e.g. substituted by a lower alkoxycarbonyl group).

The herbicidal activity of the compounds according to the invention is evident from the following test results. Herbicidal action under glass before plant emergence.

An aqueous suspension of the following composition was made: substance to be tested 40 mg Tween 80 50 mg

Distilled water with 0.1% w / w Scurol 0 to 40 ml to which the active ingredient was ground and suspended in water containing the Tween 80 and the Scurol O- (Tween 80 is polyoxyethylated sorbitan monolaurate; Scurol O is a poly- oxyethylated alkylphenol, mainly octylphenol with 10 ethyleneoxy units).

The aqueous suspension described above was diluted, if necessary, to the desired concentration with distilled water containing 1% Scurol O. Pots 6.5 cm in diameter and 8 cm in height were filled with a mixture of equal parts of silty clay and river sand. In each pot 30 seeds of one of the following varieties were placed:

Symbols

30 Wheat (Triticum sativum), var. Caton TW

Foxtail (Alopecurus myosuroides) USA

Early oats (Avena fatua) WH

Lentil (Lens culinaris), var. "Large blonde" LN

Radish (Raphanus sativus), var. Round and rose 35 with white head RAD

Fodder beet (Beta vulgaris), var. Cerès BT

Lettuce (Lactuca sativa), var. "gotte jaune d'or" SLA

Buckwheat (Polygonum fagopyrum) BW

Amaranth (Amaranthus caudatus) AMA

8402312 A * - 4 -

The pre-treatment was done by spraying the aqueous suspension of the active substance at the desired concentration on the seeded surface, each jar receiving about 0.3 ml. The surface was then allowed to dry and the seed was covered with an approximately 2 mm thick layer of soil.

Twice a day the pots were watered by sprinkling and kept at a temperature of 22-24 ° C and a relative humidity of 70-80%, under artificial lighting of about 5000 lux on the plant surface, 10 for 16 consecutive hours per 24 hour.

21 days after this treatment, the number and height of the live plants were recorded, both in the treated pots and in the blank pots (which had been treated in exactly the same way, except that there was no active substance in the aqueous spray liquid). The percentage of living plants in relation to the blank (% N) and the average height of the plants, also in relation to the blank (% H), were thus determined. By multiplication, the percentage growth relative to the blank was found: 20% N x% H 100

The final results thus obtained are shown in Table A. Here the figure 0 corresponds to a full herbicidal action and the figure 100 means that there was no effect at all.

Herbicidal action under glass after the emergence of plants ♦

This was determined in the same way as the pre-emergence herbicidal activity, but with the following differences: - after sowing, cover with an approximately 5 mm thick layer of soil, place the pots in the greenhouse and leave grow to the following stages: up to 2-3 leaves with wheat, foxtail, lettuce and amaranth, up to 3 real leaves with lentils, 35 and well spread cotyledons with buckwheat, beets and radish, 8402312 * ♦ * - 5 - - in the post-treatment (or "post emergence" as some say) the active ingredient solution or suspension was atomized over the plants and the plants were then allowed to dry.

As with the pre-treatment, the results were recorded 21 days after the treatment, again comparing with the blanks in the same way. The results of this are shown in Table B.

Herbicidal action under glass and selectivity on weeds over cultivated crops.

This happened in the manner described above, but now with the following types:

Cultivated crops RICE Rice (Oryza sativa) 15 TW Wheat (Triticum vulgare)

Weeds VS Foxtail (Alopecurus myosuroides) HP Coot (Echinochloa crus-galli) RG Rye grass (Lolium multiflorum) 20 NA Needle (Setaria viridus) FB Velvet leaf (Abutilon theophrasti) SI Side (Sida spinosa) Chrysanthemum marigold matricarioides) 25 ER Great speedwell (Veronica persica) SW Narrow-leaved plantain (Piantago lanceolata) AM Foxtail amaranth (Amaranthus caudatus) ZN Black nightshade (Solanum nigrum) WM White mustard (Sinapis alba) 30 AW Field bindweed (Convolvulus arvensis) DS Everyday purpurea) VM Bird Wall (Stellaria media) XP Xanthium (Xanthium pennsylvaticum)

Again the percentage growth was determined relative to that of the blank; the results are shown in table C.

8402312 - 6 -? Κ *

Herbicide pre-application on various species.

Various types were sown in pots of 9 x 9 x 9 cm with light garden soil (number of seeds depending on the size of the grain). These pots were misted with an amount of liquid corresponding to 500 l / ha and concentrations of active substance such that the doses thereof were 2 or 0.5 or 0.125 kg / ha. So that treatment was done on non-soil, covered seed.

The liquid used for this purpose was an aqueous suspension of the active substance further containing 0.1 wt% Cemulsol NP 10 (polyoxyethylated alkyl phenol, mainly gp nonylphenol) and 0.04 wt% Tween 20 (polyoxyethylated sorbitan oleate). To prepare this suspension, the ingredients were in one. micronizer so that the average particle size was below 40 µm.

After the treatment, the seed was covered with about 3 mm soil, the pots were placed in trays arranged for watering from below, and the whole was kept at room temperature at 70% relative humidity for 21 days.

After 21 days, the numbers of live plants in the treated pots were counted and compared with the numbers in the blank pots; here too 0% corresponds to a total herbicidal effect. The results of this are shown in Table D. 25 Herbicide application to various types of nê. stand up.

Various types were sown in pots of 9 x 9 x 9 cm with light garden soil (number of seeds depending on the size of the grain). The seed was then covered with about 3 mm of garden soil and allowed to germinate and grow into plants of appropriate size. This was in the grasses to the formation of the second leaf, in the soybeans to the development of the first three-part leaf, and in the other dicotyledons to the full development of the cotyledons and the development of the first true leaf. The 35 pots were then misted with an amount of liquid corresponding to 500 l / ha and with an active substance concentration such that the dose thereof was 2 or 0.5 or 0.125 kg / ha. So that treatment was done on covered seed.

The liquid used for this was prepared in the same manner as described above. The 5 pots were placed back in trays arranged to deliver water from below, in which the plants were grown for 21 days at ambient temperature and 70% relative humidity. After those 21 days, the growth outcomes were recorded again and compared with the growth of the blanks. The outcomes of this are also shown in Table D.

The compounds according to the invention generally exhibit an excellent action against dicotyledons that are yet to emerge, but especially against weeds that are already there, and in particular against weeds that are important in soy cultures, such as velvet leaf, diaper clean and Xanthium .

The invention also relates to a process for the preparation of compounds of the formula I and their salts to be used in agriculture. This preparation takes place in a manner known per se for analogous compounds.

The compounds of formula 1 can be prepared by reacting a phenyltetrazole of formula 2, wherein W and R have the aforementioned meanings and A represents a hydroxy group or a halogen atom (preferably fluorine or chlorine) with a compound of formula 3 , Wherein X, Y and D have the meanings given previously and B represents a halogen atom (preferably fluorine or chlorine) or a hydroxy group, with the proviso that B is other than A, ie that or B is a halogen atom and A is a hydroxy group or B is a hydroxy group and A is a halogen atom.

If it is desired to prepare a compound of the formula 1 in which W is a hydrogen atom, the starting material is preferably chosen as a phenyltetrazole of the formula 2 in which A is a hydroxy group and a compound of the formula 3 in which B is a halogen atom.

If it is desired to prepare a compound according to formula 1 in which W represents a nitro group, the starting material is preferably chosen as 8402312 »- 8 -», »- - a phenyltetrazole according to formula 2 in which A is a halogen atom and a compound according to formula 3 in which B is a hydroxy group.

The reaction of compound of formula 2 with compound of formula 3 generally takes place in the presence of a basic substance, at a temperature between 80 ° and 180 ° G and in an aprotic polar solvent, such as dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl-2-pyrrolidone, acetonitrile or acetone. The basic material used is advantageous sodium or potassium hydroxide or carbonate. Incidentally, the compounds of formulas 2 or 3 having a hydroxy group can also be used as a preformed alkali metal salt.

The phenyl-15-tetrazole of formula 2 to be used as starting material can be prepared by the action of NaN 2 on a nitrile of formula 4 in which A and W have the meanings given previously, with the limitation that as W is a nitro group A necessarily must be a halogen atom. That reaction occurs in the manner described by K. Kadaba 20 in Synthesis (1973) biz. 71-84. A phenyltetrazole of formula 2 is then obtained in which R is a hydrogen atom.

Phenyltetrazoles of formula 2 wherein R is a substituent other than hydrogen can be prepared from the phenyltetrazole just mentioned by the action of a reagent of the formula RT in which R may have the previously given meanings and T an leaving group such as a halogen atom (preferably iodine or bromine) or an aryl sulfonate group (such as benzenesulfonyloxy, toluene sulfonyloxy or xylene sulfonyloxy).

The compounds of formula 1 wherein W represents a halogen atom or a nitro group can also be obtained by halogenation or. nitration of a compound of formula 1 wherein w is a hydrogen atom and X, Y, D and R may have the aforementioned meanings.

The nitration of a compound of formula 1 in which W = H can be carried out with the usual nitrating agents such as nitric acid and potassium nitrate in the presence of sulfuric acid, optionally in an inert organic solvent, advantageously a chlorohydrocarbon such as methylene chloride, perchlorethylene, chloroform, etc., and generally at low temperature (thus between -20 ° and + 20 ° C). For example, the halogenation of a compound of formula 1 wherein W = H can be done with a halogen in a solvent such as acetic acid, with reflux heating.

Compounds of formula 1 wherein 10 W and R are both hydrogen can also be obtained by the action of NaN 2 on a nitrile of formula 5 wherein X, Y and D have the meanings given previously, also by the above-mentioned method of K. Kadaba.

Compounds of formula 1 wherein R is a substituent other than hydrogen can also be prepared from a compound of formula 1 wherein R = H and W = H by acting on that compound a reagent of the formula RT, wherein R and T are the have the aforementioned meanings. This reaction generally takes place in an inert organic solvent at a temperature such as between 20 ° and 150 ° C.

As already indicated, the salts of the compounds of formula 1, wherein R is a hydrogen atom, can be obtained by treating those compounds with a suitable base, preferably with NaOH.

At the end of the reaction, whatever it is, the compound of formula 1 or its salt is separated from the reaction mixture by conventional techniques, for example, by distilling off the solvent or by crystallization. If necessary, the substance is then purified by conventional techniques, such as by recrystallization from an appropriate solvent or by liquid or vapor phase chromatography.

The invention is further illustrated by the following non-limiting examples. The structure of the disclosed compounds was characterized by infrared 8402312-10 * spectrum, NMR spectrum and elemental analysis.

Example I

Preparation of 5- / 3 '- (2' - chloro-4 '' - trifluoromethylphenoxy) -phenyl / tetrazole (Compound No. 1) 5 150 ml of methanol and 13.2 g of KQH were added to a 1 liter three-necked flask as pellets, and then all of a sudden 18 g (0.1 gmole) of 5- (3'-hydroxyphenyl) tetrazole (with 1 mole of crystal water), keeping the temperature below 30 ° C. The mixture was kept at that temperature for about 1 hour, after which the solvent was distilled off under a pressure reduced to about 1 millibar. The potassium salt of 5- (3'-hydroxyphenyl) tetrazole was thus obtained as brown oil.

This brown oil was dissolved in 100 ml of dimethyl sulfoxide and 21.5 g (0.1 g mol) of 3,4-di-chloro (trifluoromethyl) benzene was added thereto, and the mixture was heated to 130 ° C for 5 hours. After cooling to room temperature (about 25 ° C), the reaction mixture was poured into 500 ml of water.

The water phase was extracted with 2 x 100 ml of methylene chloride. Then, in the aqueous phase, the pH was adjusted to 1 with concentrated hydrochloric acid. Crystals of unreacted tetrazole and an oil which was dissolved in 200 ml of methylene chloride were now separated. The resulting organic phase was washed several times with water, dried over Na 2 SO 4 and finally evaporated to dryness. The oil thus obtained was stirred with 100 ml of water. The resulting dark-colored crystals were filtered off with suction, washed with water, dried in an oven and finally recrystallized from water / ethanol 1: 1. There was thus obtained 13.2 g (38%) of compound No. 1 according to formula 1 (X = CF ^, Y = Cl, D = -CH =, W = H and R = H), m.p. 173 ° C.

The 5- (3-hydroxyphenyl) tetrazole used as starting material was prepared by the action of NaN 2 on 3-cyanophenol in dimethylformamide, in the presence of ammonium chloride, analogous to the procedure described in Synthesis (1973) pp. 71- 84.

Compound No. 1 was also prepared in another manner, as follows: 8402312 \ - 11 - *

17.6 g (0.059 gmol) of 3- (2'-chloro-4'-trifluoromethylphenoxy) benzonitrile, 4.2 g (0.065 gmol) NaN 2, 3.4 g (0.065 gmol) ammonium chloride and 30 ml dimethylformarri were placed in a three-bulb flask rde. The reaction mixture was kept at 100 ° C for 4 hours. After cooling to room temperature, it was poured into 500 ml of water. A solution was obtained in which the pH was adjusted to 1 with 6N hydrochloric acid and stirred for 10 minutes. A white precipitate formed which was filtered and washed with water. After air drying, 19.5 g of compound No. 1 were obtained.

The 3- (2'-chloro-4'-trifluoromethylphenoxy) -benzonitrile was prepared by the action of trifluoroacetic anhydride on 3- (2'-chloro-4 '-trifluoromethoxyphenoxy) benzamide. Example II

Preparation of 5- / ~ 2'-nitro-5 '- (2 "-chloro-4" -trifluoromethyl-phenoxy) phenyl / tetrazole (Compound No. 2).

9.2 g (0.027 gmol) of compound No. 1 were dissolved in 40 ml of concentrated sulfuric acid and 40 ml of 1,2-dichloroethane were added thereto. While the temperature of the reaction mixture was kept at 0 ° C with stirring, 2.7 g (0.027 gmol) of potassium nitrate were added gradually over 15 minutes, after which the mixture was stirred for an additional hour at that temperature and finally for 1 hour. room temperature.

This reaction mixture was poured into 400 g mixture of ice and water. After extraction with 2 x 100 ml of dichloromethane, the organic phase was dried and evaporated to dryness. There was thus obtained 8 g (78%) of an 80:20 mixture of 5-f-21-nitro-51 - (2 "-chloro-4" -trifluoromethylphenoxy) phenyl J-tetrazole and 5- / 2 ' nitro-3 (2 "-chloro-4" -trifluoromethyl-30-phenoxy) -phenyl-tetrazole.

Chromatography on silica with ethanol / C12 / acetic acid 1.5: 15: 0.1 gave 4.2 g (47%) of the former (compound No. 2) with snip. 142 ° C, and 0.4 g of the latter substance, m.p. 206 ° C.

35 8402312 *% *

Example III

- 12 -

Preparation of the sodium salt of compound No. 2 (compound No. 3). _

1.16 g of compound no. 2 were dissolved in 10 ml of water containing an equivalent amount of NaOH.

This solution was evaporated to dryness under vacuum at 60 ° C to give 0.9 g (75%) of the desired product, a yellow substance of the formula E structure and melting point above 250 ° C. Example IV

Preparation of 2-methyl-5 - / "* 2'-nitro-5 '- (2" -chloro-4 "-trifluoro-methylphenoxy) phenyl / tetrazole (compound No. 4a) and 1-methyl-5- / 2'-nitro-5 (2 "-chloro-4" -trifluoromethylphenoxy) -phenyl / tetrazole (Compound No. 4b).

In a 250 ml three-necked flask, a mixture of 7.72 g (0.02 gmol) of compound no. 2, 14.2 g (0.1 gmol) of methyl iodide, 50 ml of dimethylformamide and 2.76 g (0, 02 gmol) anhydrous potassium carbonate heated at 70 ° C for 15 hours. The solvent was then distilled off under partial vacuum (10 millibar) and the residue was taken up in 100 ml water and 2 x 20 100 ml methylene chloride. The organic phase was collected and dried over Na 2 SO 4. After evaporation to dryness under vacuum, there was 8 g of oil which was chromatographed on silica gel with diisopropyl ether. Thus, 5.1 g (63%) of compound No. 4a (structure of formula 7a and mp. 90-92 ° C) and 0.5 g (6%) of compound No. 4b (structure of formula 7b and mp. 148 ° C).

In another preparation, Compound No. 4a was obtained in 72% yield by nitriding 2-methyl-5- / ~ 3 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenyl / t etrazole (mp 80 ° C) which was itself obtained by alkylating compound No. 1.

Example V

Preparation of 2-methyl-5- / "" 2'-nitro-5 '- (2 ", 4" -dichlorophenoxy) -phenyl / tetrazole (Compound No. 5).

In a 100 ml three-necked flask, a mixture of 5.4 g (0.024 gmol) of 2-methyl-5- (2'-nitro-5'-fluorophenyl) -tetrazole, 3.9 g (0.024 gmol) of 2, was added. 4-dichlorophenol, 3.3 g (0.024 8402312 * - 13 gm 2 K 2 ° 3 and 50 ml dimethylformamide stirred at room temperature for 30 minutes and then heated at 80 ° C for 7 hours. vacuum evaporated The oil left over was taken up in 150 ml CS 2 Cl 2 and then washed with 3 x 50 ml 5 water The organic phase was dried over Na 2 SO 4, filtered and evaporated, and the yellow oil which was left over an equal mixture of diisopropyl ether and hexane crystallized After filtration, rinsing with 2 x 15 ml of diisopropyl ether, suction-drying and air-drying, there was obtained 5.8 g (66%) of the expected compound (formula 8 wherein X =

Cl, R = CH 3) with mp. 115 ° C.

The 2-methyl-5- (2'-nitro-5'-fluorophenyl) tetrazole used as starting material was prepared by 5- (2-nitro-5-fluorophenyl) tetrazole in acetone in the presence of K 2 CO 2 with 15 CH 2 J to alkylate. This 5- (2-nitro-5-fluorophenyl) tetrazole was itself obtained by nitriding 5- (3-fluorophenyl) tetrazole with nitric acid.

Examples VI through XV

In the manner of Example IV, starting from the appropriate starting materials, compounds Nos. 6 to 15 were prepared (the compounds have the same Nos. As the Examples).

All the compounds prepared, except No. 4b, are according to formula 8, and an overview of those compounds with their melting points (or else their spectral characteristics) and the yields of their preparations are shown in Table E. Of the compounds with an asymmetric carbon atom there are two enantiomeric forms R and S. As already mentioned, both forms and also the racemates are within the scope of the invention.

The following compounds can be prepared analogously to the procedure of Example IV: 2- (1-methoxycarbonylethyl) -5- / 2'-nitro-51- (2 "-chloro-4" -trifluoromethylphenoxy) phenyl-tetrazole ( the R enantiomer), 2- (1-methoxycarbonylethyl) -5- / 21-nitro-5 * - (2 "chloro-4" -35 trifluoromethyl) phenoxy tetrazole (the S enantiomer), 2- (1 -methoxycarbonylethyl) -5- / 21-nitro-5 '- (31'-chloro-5' '- trifluoromethylpyriol-2 "-oxy) phenyl tetrazole (racemate and also 8402312-14 -, the separate forms R and S) .

For their practical application, the compounds of the invention will generally be used in the form of preparations, which are also within the scope of the invention.

These preparations usually contain, in addition to the active substance (compound of the formula 1), one or more solid or liquid carriers or diluents that are acceptable in agriculture and one or more agents which are also acceptable in agriculture, if necessary they may also contain other contain acceptable allowances in agriculture.

Usually the compounds will contain 0.05 to 99% by weight of active ingredient and 0.01 to 20% by weight of surfactant and 1 to 99.95% carrier.

As solid carriers, one can mention the natural and synthetic silicates, such as diatomaceous earth, clay, talc, attapulgite, vermiculite, kaolin, montmorillonite and calcium aluminum silicate, calcium carbonate, natural resin or synthetic resin such as polyvinyl chloride, etc.

As liquid carriers, water and alcohols such as isopropanol, glycols, ketones such as acetone, butanone, 4-methylpentanone-2 and cyclohexanone, ethers, aromatic and arylaliphatic hydrocarbons such as benzene, toluene and xylene, petroleum fractions such as kerosene, chlorine-25 can be used. hydrocarbons such as carbon tetrachloride and perchlorethylene, etc.

When the carrier is water or a conventional organic solvent, the compositions of the invention advantageously also contain surfactant. This can be an emulsifier, dispersant, flocculant or humectant, ionic or just non-ionic.

As surfactants it is advantageous to use condensation products of ethylene oxide with fatty acids, fatty acid amides, fatty alcohols, fatty amines or substituted phenols (in particular alkyl phenols or aryl phenols). Also advantageous are fatty acid esters of sorbitan and sucrose derivatives, alkali metal or alkaline earth metal salts of lignin and alkylaryl sulfonic acids, salts of esters of sulfobamic acid, alkyl hetalnes and using sulfobetaxnes, etc.

5 The work "Mc Cutcheon's Detergents and

Emulsifiers 1975 Annual "(MC Publ. Corp. of Ridgewood, New Jersey, USA) describes numerous surfactants and makes recommendations for their use.

US Pat. No. 3,713,804 also describes numerous anionic, cationic and non-ionic surfactants for agricultural use. The surfactant to be used in the compositions of the invention is advantageously selected by those skilled in the art from the above groups of substances.

In addition to the active ingredient, the carrier and the surfactant, the compositions of the invention may also contain other additives such as non-surfactant dispersants, peptizers, colloid protectors, thickeners and adhesives which improve rain resistance, stabilizers, preservatives, anti-corrosion materials, dyes, metal binders and anti-foaming, caking and gelling agents, etc.

The preparations according to the invention can take various solid or liquid forms.

As solid preparation forms one can mention the dusting powders (with contents of active substance up to 100%), granules and micrograins, in particular obtained by extrusion, by compression, by impregnation of a granular carrier or by granulation of a powder (wherein the active ingredient content is between 1 and 80%). In the end, these solid forms are usually used dry, without any dilution.

As formulations that are ultimately used as liquids, one can use wettable powders (or powders to be atomized), emulsifiable solutions or concentrates, concentrated suspensions (or "flowables"), solutions (especially in water) and emulsions and dispersions to mention.

The dusting powders usually contain from 0.1 to 5% by weight of active substance, an inert carrier (which may be an impregnation carrier such as silica gel) and, if necessary, from 0 to 10% by weight of stabilizer and / or other auxiliary material. for better penetration, an adhesive, a dye or something against clumping. They are usually prepared by mixing the active ingredient with the inert carrier and grinding the mixture thoroughly.

The granules and microbeads, usually with a low active ingredient content, can be prepared beforehand and then impregnated, or prepared in bulk, for example by spray drying or by extrusion. In the latter case, a binder and surfactant must also be added to ensure rapid release to the soil. They generally contain 0.5. up to 100% by weight of active ingredient and 0 to 10% by weight of excipient such as stabilizer, slow release agent, binder and / or solvent.

The wettable powders (optionally to atomize 20) are usually prepared to contain 20% to 95% active ingredient, in addition to the solid carrier, 0 to 5% wetting agent, 3 to 10% dispersant and, if necessary .0 to 10% stabilizer and / or other auxiliary substances, such as for better penetration or anti-clumping, an adhesive, a dye, etc.

For example, the composition of a wettable powder of 50%: active ingredient 50% sodium lignin sulfonate 5% 30 sodium dibutylnaphthalene sulfonate 1% clay (kaolin) 44%

Another example of a wettable powder has the following composition: 35 8402312 - 17 -

V

t active substance 50% sodium and / or calcium lignin sulfonate 5% (flocculant) --- * '^. isopropylnaphthalene sulfonate 1% 5 silicic acid (anti-caking) 5% kaolin (filler) 39%

In order to obtain these dusts or wettable powders, the active substance is intimately mixed in a suitable mixer with the other constituents and the whole is ground in appropriate moles and s-Aidus * powdered matter of which the wettability and the contents are obtained. suspension can be done easily (so with advantage); they can be suspended in water at any concentration, and such a suspension can advantageously be applied to the leaves of the plants.

The emulsifiable solutions or concentrates contain the active ingredient dissolved in some liquid (generally an aromatic hydrocarbon) and additionally, if necessary, an auxiliary solvent, which may be a ketone, an ester, an ether oxide, etc. In general, these liquid preparations contain 5 to 60% (by weight or by volume) of the active substance and 2 to 20% of the emulsifier, and can be prepared, for example, by dissolving the active substance and the emulsifiers in the liquid or mixture of solvents , stirring well and heating or cooling.

Starting from those emulsifiable solutions or concentrates, one can obtain emulsions of any desired concentration by diluting with water, which are particularly suitable for applying the compounds according to the invention.

The concentrated suspensions (or "flowables") are suspensions of fine solid particles of the active ingredient in water or a non-dissolving oil, prepared to be stable products that do not settle. They usually contain 10 to 75% by weight of active ingredient, 0.5 to 15% surfactant, 0.1 to 10% thixotropic agent and 0 to 10% appropriate adjuvant, such as against foaming or corrosion 8402312 \ v - 18 - or for a better penetration, a stabilizer or an adhesive, and as carrier water or an organic liquid in which the active substance has little or no solubility: certain solid organic or inorganic substances can be dissolved in such a carrier in order to settle or prevent gelling.

These concentrated suspensions are prepared by finely grinding the active substance and then dispersing it in the carrier liquid already containing the auxiliaries, after which the dispersion is ground in a ball mill.

From these concentrated suspensions, suspensions of any desired concentration can be obtained by diluting with water.

The above-mentioned aqueous suspensions or emulsions of the active substance and all those other preparations also fall within the scope of this invention.

The emulsions can be water-in-oil and oil-in-water type, and they can have a thick consistency such as mayonnaise.

Finally, the invention also relates to a method for the selective control of weeds between useful crops, in particular between rice and wheat. This method is characterized in that a pre-weed active, but not phytotoxic dose of a compound of the formula I is applied to the soil before the beneficial crops have emerged. The dose to be used varies with the chosen compound, the useful crop, the climatic conditions and the weeds to be controlled.

30 8402312 4 * - 19 ·· - rt Lfi o o o o o.o

S H

soo ^ oo ^ o CQ io o for ovo

H W

* c o VO O Ol O O <r> J O -rt O r-t CO ^ B r-f'i'si'voomma on ^ in o

Qor'iflo omm sc o eg σι o <-i (5 »« w 2 ui a in o η o ΰ i4 co ΟΙ (Ό O ^ 51 O <3 o O ._--------- - mc (Ö (Ö * · oo EB in in vo «) 'O o _, o> in o- · <γ ~ co σι oo> ® ws 1> --------- a: ·

m °. co vo O »O ·« '04 n O

jg 4j> rooi wroco o

<U -H> Ü (B

-A O ----------

O M

• ί-ί {Ti

o SOlO ^ pOOOO

YYyyP Eh coc ^ foaocoeoo 0) S ___.____ 01 <tf

HflOotMHrtfiH

cn \ o b> oi Q Ai ö «ö

• lw »-ι ΟΙ · <3 · CO O 'CO O

o ^

YOU

co 8402312 -2Ö - S- I O O O O o <- <Λ si 000 <3 <0 <N0 a o <- <

Onion H

Eh [- · O O Γ0 O O <3 <

PQ ID r-i tH

Q ooooinoo

C sS W

Φ «

O O

a § —----- O <d

r-H

Λ fl S ui cn r- co r- co <31

ö hJ Γ 'O <-) O LD

0) ω t; <d _____ μ · w o> H 'd) K o ffi o η <n η o n o A φ> oc ^ cNi-'cacoo <0 <0 -Μ <η <η

And β Ο · Η Ο) ÖÏ ο - 1- C »Μ • Η θ 'Ui ο ο ο ο <a <m co Λ> old <- <mt" · co Μ dP <Η Φ S__ S o σ' r ~ ο η ο

Eh ooor ^ ocoo

t-1 r-4 r-H

* id * H ^ O CN * -H rH r * H r — 4 03 \ vH *

0 C7> CN

Q X

•

SH

c

MH

0 Id

+ J r-iOJ <3 <OC ^ COO

CO tH

8402312 *! S- - = '- 21 -

Table C

Herbicide under glass nè. turnout% relative to the blank

Compound no.3 no, 4a, no.8

Dose kg / ha_ 0_i5_0 ^ 5_0.5

Oryza sativa 54 88

Triticum vulgare 100 61 85

Alopecurus myosuroids 13 67

Echinochloa crus-galli 34 46

Setaria viridus 96 0 15

Abutilon theophrasti 50 0 47

Sida spinosa 20 20

Chrysanthemum annuum 23 80

Macricario matricaria 15 15

Veronica persica 0 0

Plantago lanceolata 0 4

Amarantus Caudatus 0 0

Solanum nigrum 8 00

Sinapis alba 0 0

Convolvulus arvensis 0 3

Stellaria media 7 54 8402 312 - 22 -

Soooooooo ooooooo cü m m m

Sooooooooooooooo And cm ooooooooooooooo soomommooooo oooo

r — ΐ .—! t — I. — f rH t — I t — 1 rH rH rH '1 rH

Soooooooooooooom IH so oooooooooooooo

xH tH tH tH rH tH tH tH tH tH tH tH H

you .... ..............

0) —— —— - - ---- ““

+ J OOOOOOOOOOOOOOO

JÜ 030000 0-0000000000

U QtHtH ^ HtHTHTHtHTHtHrHtHtHtHtH

sC ____; _____.__________ pqmoooooooooooooo

feOOQOOOOOOOOOOonCN tH tH tH tH tH

CD- OOOOOOOOOOOOOOO

Ci CM CM m m CM CM

S OOOOOOOOOOOOO OO WlOmCMOtmCMOOCyimmcNCOCM

rH rH

SOOOOOOOOOOOOOOO

e> m SO OOOOOOOOOOOOOO ^ tj1

OOOOOOOOOOOOOOO

S o m o o oin m m

tH tH tH tH

Q _________________ 'm oooooooooooooom 5 Soocooocoooooooo oo

'H S ή rH rH rH rH rH rH rH rH rH rH

E- <---__--- r ------------- 03000000000000000 Otno mm to mm i>

tH

ooooooooooooooo in pqoocoooooooo mcocn

(¾ pq τΗ τΗ tH tH ^ tH tH tH tH

u o ------------------ o> 0000000000000000 pi cm m cm o m cm

rH

sooooooooooooooo EB o cd m o o go co cm om

rH rH rH rH

m m m m m and (ö cm cm cm cm cm

• rH jfj m rH m <H m »H mrH m rH

CT3 Ö —h. 11 - - »» «·»

OHCNCMOOCMOOCMOOCMOOCMOO

O

* 8402312 r m

> IW rH rH

O O Ή CM

O 4-) rH rH

S 03 0 mr * - 23 - o r-

CM

co n * -t vo m m m f- _ I [CM (η n. co n * cd n _j

0 CM I> r- <«O

- G

1 <d <m co ** o

at a co CM

5 5 - * * <o cö c o m o mo .3 g Yy o ^ § N Μ N,. fi vó co có ω o $ mds - 4¾ g w CM O Hl λ z g i i * £ a I i h 5 0) S3 id

O P

o - + J

• co cm o cm tn t "<u t ~~ © o cm © © cm 5 + J

Q, [^^ ΐΛ ^ ΗΙβτί ΝΉ ^ ΓΟ'ΠτίΠτΙ g i-l ι-H CM 1- * r-1 · * —I, —t ^ * “* ^ 03 V 00 0 0 0> * 0 •

co-P

o 4J a * - ·

H c CU I

3 <u EP S

SS-- ^ CU

h Sdpcooinnvaint ^ oicii ^ iniai-fi-vr ', H

O ^ s_it * 3 ^ t.r'vo vOMi'ninvocniavor'vo, df> C

4-1 C -1 - (- 1-) © 2 _

ra p $ Λ C

d O © © ra <- (

0> P H

f— {© cd

0> -P

-1-V I © H 01 03 pj o> fi J * 03 '© 4-1

na) (S 45 S -P

© O »- 'K _ 0 O

o Ü ^ 4-) O '© • η ininmcoMn § 3 B B B, «B n Ö p ©

e CM CM CM ® U B- O QjO

• h UOinyaoCJcM1 ^

A tQOBQQOQB © C

Ή inc ^ O OcMOOUOU Ό © © cocottJECCJOÜUCJ - O cm> «KBcdKE cm co cm ^ ö cm in <n EB c ©

SOUUOK co O B mBffiU -n-H

© (I I t O BB U O B .CM- U O -r) ft

43 -P I U I CM a ü l cm N I

-H - EB w - 'EB ώ © ECJBBUch U O I O U I © © H © «© 43

O 'C

CM CM cm cm cm cm cm cm cm cm cm cm cm CM jq> 2 EBOOOOOOOQOOOOOO | sëëszsssssazszs ~

2 C

S <u> © © co co co co cocococococococo co co η-j 6.6161041¾¾¾¾¾¾¾¾¾¾¾ © ouooauaooouoouu dov © ft

> O

a

P ·> c ^ eMcoMi'in <ai> co <J'OwcMco ^ in τ-i t “H i ▼“ * <- * "<8402312

Claims (17)

1. Compounds having a herbicidal action, characterized in that they are compounds according to formula 1, wherein X represents a halogen atom or a lower alkyl group substituted by one or more halogen atoms, 5. a hydrogen or halogen atom or a group CF ^, CN, NO2 or CH2, D represents a nitrogen atom or the group -C (Z) =, wherein Z is a hydrogen or halogen atom, W represents a hydrogen or halogen atom or a nitro group, 10. a hydrogen or halogen or an optionally substituted aliphatic or aromatic, alkylthio, amino, acyl, alkylsulfonyl, arylsulfonyl, hydroxy, or cyano group, and its commercially acceptable salts. 2. Compounds according to claim 1, characterized in that R is a group substituted by halogen, alkoxy, hydroxy, lower acyl, carboxyl or carboxylate. 3. A compound according to claim 1 or 2, characterized in that R represents a hydrogen or halogen atom or an optionally substituted alkyl, aryl, lower alkenyl, lower alkynyl, lower alkylthio or amino group, or a group -CO-R 'where R' is a hydroxy, lower alkoxy, aryloxy or amino group, the latter of which is optionally again substituted, or a group -SO 2 -R "wherein R" is alkyl, aryl, hydroxy or is cyan. 4. A compound according to any one of the preceding claims, characterized in that in formula 1 X = CF3, Y = Cl, D = -CH =, W = NC> 2 or H, and that R is an optionally substituted alkyl group . 5. A process for the preparation of a compound according to any one of the preceding claims, characterized in that a phenyltetrazole according to formula 2, wherein W and R have the aforementioned meanings and A has a hydroxy group or a. is halogen, react with a compound of formula 3 wherein X, Y and D have the meanings given previously and B is a halogen or hydroxy group, with the proviso that B is other than A and that a hydroxy group may also be in the form of a phenolate, 6. Process for the preparation of a compound of formula 1, wherein W is a halogen atom, characterized in that a compound of formula 1 in which W = H, and wherein X, ï, D and R have the meanings given previously, halogenates. 7. Process for preparing a compound of the formula 1 in which W = NC> 2, characterized in that a compound of the formula 1 in which W = H and in which X, Y, D and R have the meanings given previously is nitrated , A process for preparing a compound of formula 1, wherein W = H and R = H, and wherein X, Y and D have the meanings given previously, characterized in that a nitrile of formula 5 is reacted with NaN ^ - 9. Process for preparing a salt of a compound of formula 1 wherein R = H, characterized in that a compound of formula 1 in which R = H is reacted with an appropriate compound, preferably with NaOH. 10. Process for preparing a compound of formula 1 wherein R is other than hydrogen and X, Y, D and W have the meanings given previously, characterized in that a compound of formula 1 in which R <H> is left react with a reagent of the formula RT. 11. Herbicidal composition, characterized in that the active substance contains one or more compounds according to any one of claims 1 to 4. Preparation according to claim 11, characterized in that it contains one in addition to the active substance. or more solid or liquid agricultural acceptable carriers and one or more agricultural acceptable surfactants. 84 02 3 M t »Fr - 26 - '13. Preparation according to claim 12, characterized in that it contains 0.5 to 95% active substance. 14. A composition according to claim 13, characterized in that it contains 1 to 95% carrier and 0.1 to 20% surfactant. Method for the selective control of weeds, characterized in that an effective dose of one or more compounds according to any one of claims 1 to 4 is applied on site. A method according to claim 15, characterized in that a preparation according to any one of claims 11 to 14 is applied, at a dose between 0.01 and 5 kg / ha (preferably between 0.1 and 2 kg / ha ) of active substance. Method according to claim 15 or 16, 15, characterized in that the selective weeds are controlled between soybeans. 8402312 S »! ·» IW> ^ NN y cC —a ~ r 1, Y <IN = B ^ NN 13 1 b .— (^ N — N '# 2 “' f · -4 ·. R 4 io ^ NN D. X— '/ - <Cl, - / C ^ N — N Na © ^ C? - (Q) -tM ^^ hN0 = 6 xN-N-CH3 7a ^ NN α ||. N - N- R / p ^ A / P ~ \\ ^ N — N CL cC 1 CFs \ 0/0 \ 0 / NQi 1 N = N 8402312 8 RHONE-POULENC AGROCHIMA, Lyon, France _