FR2549831A1 - NOVEL ARYLOXYBENZOIC ACID DERIVATIVES AND THEIR USE AS HERBICIDES - Google Patents

Abstract

THE INVENTION CONCERNS NEW DERIVATIVES OF ARYLOXYBENZOIC ACIDS. THESE COMPOUNDS RESPOND TO FORMULA I BELOW: (CF DRAWING IN BOPI) IN WHICH THE SYMBOLS USED HAVE THE FOLLOWING MEANINGS RESPECTIVELY: X: HALOGEN OR LOWER ALKYL POSSIBLY HALOGEN; Y:

Description

The invention relates to novel herbicidal compounds containing a tetrazole group,

  Derivatives of aryloxybenzoic acids It also concerns the preparation of these new compounds as well as the compositions for agricultural use containing them. Nitro-2 (2-chloro-trifluoromethyl-4-phenoxy) 1-benzoic acid, also known as acifluorfen and its salts, and their use as herbicides, are known.

  especially for the weeding of soybeans.

  Moreover, many acifluorfen derivatives have already been proposed, in particular alkyl, cycloalkyl, thioalkyl and phenyl esters, as well as mono or dialkyl amides. Such compounds are described by US Pat.

  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.

  The subject of the present invention is aryloxybenzoic acid derivatives, different from those described in

  the prior art and having excellent herbicidal activity.

  The novel compounds according to the invention are characterized in that they correspond to the general formula (I): ## STR2 ##

0 'N W

  in which: X represents a halogen atom, or a lower alkyl radical substituted by one or more halogen atoms, Y represents a hydrogen or halogen atom, or a CF 3, CN, NO 2 or CH radical; 3, z D represents the nitrogen atom or the radical -C = in which Z represents a hydrogen or halogen atom, W represents a hydrogen or halogen atom or the nitro radical, R represents the hydrogen atom or a halogen atom, or a radical chosen from the following radicals: optionally substituted alkyl (for example lower alkyl substituted with one or more of the following atoms or radicals: halogens, alkoxy, hydroxy lower acyl, carboxyl, salts and esters of this carboxyl group such as, for example, lower alkoxycarbonyls); optionally substituted aryl; Lower alkenyl; lower alkynyl; optionally substituted lower alkylthio (for example with one or more halogen atoms); optionally substituted amino (e.g., one or more lower alkyl radicals, or an acyl radical); Wherein R 'is a substituent (for example the OH radical or a lower alkoxy radical or an aryloxy radical, or the amino radical itself optionally substituted); SO 2- R "wherein R" represents a substituent (such as, for example, an alkyl or aryl radical)

or an -OH or -CN radical.

  For the purposes of this text, the adjective "lower", when it qualifies a radical means that this radical has at most 6 carbon atoms.

  The compounds according to formula (I), for which R represents the hydrogen atom, have an acid character and can therefore form, with appropriate bases, agriculturally acceptable salts. These salts can also be used as herbicides and Examples of such salts include salts of metals, preferably alkali metals such as sodium, potassium or lithium, or alkaline earth metals such as calcium or magnesium, or salts thereof. ammonium salts or mono or polysubstituted ammonium salts such as isopropylammonium; triethanolammonium, morpholinium, etc. Depending on the position of the substituent R on the tetrazole ring, the compounds according to formula (I) may exist in two isomeric forms (IA) and (IB) which are also included within the scope of the invention, and wherein the various substituents have the same meaning as in formula (I)

N N-R

y O (IA)

X_) OY J W N

x N -N

X O I 4 \ ó (IB)

R

  Among the compounds corresponding to formulas (I), (IA) and (IB), a preferred subfamily because of its remarkable herbicidal properties consists of the compounds for which: X represents the trifluoromethyl radical Y represents the chlorine D atom represents the radical CH = 35 W represents the nitro group R represents an optionally substituted alkyl radical

  (for example by a lower alkoxycarbonyl radical).

  The invention also relates to the preparation of compounds according to formula (I) and salts which can be used in

agriculture, of these compounds.

  The compounds according to formula (I) can be prepared by the action of phenyltetrazole of formula (II) the N N

C 4 R

(II)

  Wherein W and R have the same meaning as in formula (I) and A represents the hydroxy radical or a halogen atom (preferably fluorine or chlorine), on the compound of formula (III) and

B III)

X B

  in which X, Y, D have the same meaning as in formula (I) and B represents a halogen atom (preferably fluorine or chlorine) or the hydroxy radical, it being understood that B is chosen to be different from A, c that is, B represents a halogen atom when A represents the hydroxy radical and B represents the hydroxy radical when A

represents the halogen atom.

  When it is desired to prepare a compound according to formula (I) for which W represents the hydrogen atom, the other substituents or symbols having the same meaning as in formula (I), the starting materials are preferably chosen from phenyltetrazole (II) in which A represents the hydroxy radical and a compound (III)

  wherein B represents the halogen atom.

  When it is desired to prepare a compound according to formula (I) for which W represents the nitro radical, the other substituents or symbols having the same meaning as in formula (I), phenyltetrazol (II) is preferably chosen as starting materials. ) in which A represents the halogen atom and a compound (III) in

  which B represents the hydroxy radical.

  The reaction between phenyltetrazole (II) and the compound (III) is generally carried out in the presence of a basic agent, at a temperature of between 80 and 180 ° C., in a polar aprotic solvent, such as for example dimethylsulfoxide, dimethylformamide,

  dimethylacetamide, N-methyl-2-pyrrolidone, acetonitrile, acetone or other equivalent aprotic polar solvents.

  As basic agent, use is advantageously made of

  hydroxides or carbonates of sodium or potassium.

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

A W W (V)

  in which A and W have the same meaning as in the

  formula (I), provided that when W represents the nitro radical, A necessarily represents the hydroxy radical.

  This reaction is carried out according to the method described by K.

Kadaba in Synthesis 1973 p 71-84.

  Phenyltetrazole corresponding to formula (II) is thus obtained in which A and W have the same meaning.

  than previously and R represents the hydrogen atom.

  The phenyltetrazoles according to formula (II) for which R represents a substituent other than the hydrogen atom may be prepared from the phenyltetrazole obtained above, by the action of a reagent of formula (VIII)

R T (VIII)

  wherein R has the same meaning as before and T represents a leaving reactive group. The compounds according to formula (I) for which W represents a halogen atom or the nitro radical, the other substituents or symbols having the same meaning as in formula (I) can also be obtained respectively by halogenation or by nitration of the compound according to formula (I) for which W represents the hydrogen atom, and which corresponds to the formula below (IV): t NNN

X (O IV)

  in which X, Y, D and R have the same meaning as

in formula (I).

  The nitration of the compound (IV) can be carried out using a conventional nitrating agent, such as nitric acid, or potassium nitrate in the presence of sulfuric acid, optionally in an inert organic solvent, advantageously a chlorinated hydrocarbon, such as methylene chloride, perchlorethylene, chloroform, etc.

  generally operating at low temperature (between 30 -20 C and + 20 C).

  The halogenation of the compound (IV) can be carried out for example by the action of a halogen in acetic acid

heated to reflux.

  The compounds according to formula (I) for which W 35 and R represent the hydrogen atom, the other substituents and symbols having the same meaning as in formula JI) can also be prepared by the action of Na N 3 on a nitrile of formula (VI): yo CN

X X O 4 (VI)

  in which X, Y and D have the same meaning as in formula (I), according to the method of K Kadaba described above. The compounds of formula (VII) are thus obtained:

Y C 4 H

(Vii)

X-C 4 N = (VII)

  in which the various symbols and substituents have the

  same meaning as before.

  The compounds according to formula (I), for which R represents a substituent other than hydrogen, may also be prepared from the compounds according to formula (VII), the preparation of which is described above, by action on this compound of a reagent of formula (VIII)

R T (VIII)

  wherein T is a leaving reactive group such

  for example a halogen atom (preferably the iodine or bromine atom) or a radical such as the radical tosy late (or p-toluenesulfonate).

  The reaction is generally carried out in an inert organic soluent medium at a temperature in the range of 20 to

 C about.

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  As indicated above, the salts of the compounds according to formula (I) for which R represents the hydrogen atom can be obtained by treatment of these

  composed by means of a suitable base, preferably sodium hydroxide.

  At the end of the operation, according to one or the other of the processes described above, the compound (I), or the salt of this compound, is separated from the reaction mixture by the usual techniques such as, for example, by distillation. of the solvent, or by crystallization of the compound from the reaction medium. If necessary, it is then purified by the usual methods such as recrystallization from an appropriate solvent or chromatography.

liquid phase or vapor phase.

  The examples which follow illustrate the invention without however limiting it. The structure of the compounds described in these examples has been characterized by infrared spectrometry, by magnetic resonance spectrometry

  nuclear reactor (R M N) and by elemental analysis.

  EXAMPLE 1 Preparation of 1-chloro-2-trifluoromethyl-4-phenoxy-3-phenyl-tetrazole (Compound No. 1) In a three-necked 1-liter flask, 0.15 l of methanol is added and 13.2 parts are then added per portion. g of potash in pellet, then, all at once, 18 g, ie 0.1 mol of (3-hydroxyphenyl) -5-tetrazole (crystallized with 1 mole of water), while keeping the temperature below The mixture is held at this temperature for about half an hour and the solvent is distilled under a partial vacuum of about 1 millibar.

  form of a brown oil, the potassium salt of (5-hydroxyphenyl) tetrazole.

  This brown oil is then dissolved in 100 ml of

  5 g of anhydrous potassium carbonate and 21.5 g (0.1 mole) of 3,4-dichloro-trifluoromethylbenzene are added to the solution and the reaction mixture is heated at 130 ° C. for 5 hours, and the temperature is then left undisturbed.

  The reaction mixture is then poured into 500 ml of water. The aqueous phase is extracted with 2 × 100 ml of methylene chloride. The aqueous phase is then collected and acidified. H = 1 with concentrated HCl The formation of crystals consisting of unreacted tetrazole and an oil which is dissolved in 200 ml of methylene chloride is observed. The organic phase obtained is washed several times. with water and then dried over sodium sulphate. The solvent is then distilled and the oil thus obtained is stirred with 100 ml of water. The dark crystals obtained are drained, washed with water and then dried in an oven and finally

  recrystallized from 50/50 water + ethanol.

  13.2 g of 1-chloro-2-trifluoromethyl-4-phenoxy-3-phenyl-5-tetrazole, compound n 1 of formula: ## STR3 ##

Melting point: 173 C.

  The (3-hydroxyphenyl) -5-tetrazole used as starting material was prepared by the action of NaN 3 on 3-cyano-phenol, in dimethylformamide, in the presence of ammonium chloride by a method analogous to that described above.

  described in Synthesis, 1973 p 71 to 84.

  Compound No. 1 was also obtained according to a second method described below: In a three-necked flask, 17.6 g (0.059 mol) of (2-chloro-4-trifluoromethylphenoxy) benzonitrile are charged; 4.2 g (0.065 mole) of NaN 3; 3.4 g (0.065 mol) of ammonium chloride and 30 ml of dimethylformamide. The reaction mixture is brought to 100 ° C. for 4 hours,

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  The mixture is allowed to return to ambient temperature and poured into 500 ml of water. A solution is obtained, to which HCl 6 N is added until pH = 1 and stirring is carried out for 10 min. A white precipitate is formed. After filtering and then wringing with water. After drying, drying in air, 19.5 g of r (2-chloro-4-trifluoromethyl-phenoxy) -3-phenyl-5-tetrazole (compound No. 1) are obtained.

  3- (2-chloro-4-trifluoromethylphenoxy) benzonitrile was obtained by the action of trifluoroacetic anhydride on (2-chloro-4-trifluoromethylphenoxy) -3-benzamide.

  Example 2 Preparation of lnitro-2 (4-chloro-4-trifluoromethylphenoxy) -5-phenyltetrazole (compound 2) In 40 ml of concentrated sulfuric acid, 9.2 g (0.027 mol) of 1-chloro-2-trifluoromethylphenoxy-3-phenyl-5-tetrazole, the preparation of which is described in Example 1, and is added to the solution thus

  40 ml of 1,2-dichloroethane were obtained.

  While maintaining the reaction mixture at 0 ° C. with stirring, 2.7 g (0.027 mol) of potassium nitrate are gradually added over 15 minutes and then the mixture is maintained for half an hour at this temperature.

  and finally 1 hour at room temperature.

  The reaction mixture thus obtained is poured into 400 g of a mixture of ice and water. After extraction with 2 × 100 ml of dichloromethane, the organic phase is dried and the solvent is then distilled off. 78%) of an 80/20 mixture of lnitro-2 (2-chloro-4-trifluoromethylphenoxy) -5-phenyl-5-tetrazole and 1-nitro-2 (2-chloro-4-trifluoromethylphenoxy) -3

phenyll-5 tetrazole.

  Chromatography on silica (eluent: ethanol 1.5 CH 2 C 12 0.1 acetic acid) gives 4.2 g of the compound (compound 2) of the formula: ## STR2 ## Yield: 47% Melting point: 142 ° C. and 0.4 g of 1-nitro-2- (2-chloro-trifluoromethyl-phenoxy) -3-phenyl-5-tetrazole, melting at 2060 ° C. C. EXAMPLE 3 Preparation of the sodium salt of 1-nitro-2- (2-chloro-4-trifluoromethylphenoxy) phenyl-5-tetrazole (Compound No. 3) In 10 ml of water and one equivalent of 1N sodium hydroxide, it is dissolved 1.16 g of 1-nitro-2- (2-chloro-trifluoromethyl-phenoxy) -5-phenyl-5-tetrazole (compound No. 2), the

  preparation is described in Example 2.

  The water is distilled off under vacuum at 0 ° C. to give 0.9 g of the desired compound as a yellow solid, of the formula: NN Na CF 3 No C 2 Yield: 7-5% point Melting point greater than 250 ° C. EXAMPLE 4 Preparation of 2-methyl-2-nitro-2- (2-chloro-4-trifluoromethylphenoxy) phenyl-13-tetrazole (Compound No. 4A) and Methyl-II-nitro-2 (chloro-2-chlorophenyl) 4-trifluoromethylphenoxy) -5-phenyl-5-tetrazole (compound 4B) In a 250 ml three-necked flask, 7.72 g (0.02 mol) of the compound, the preparation of which is described in the example, are loaded. 2, (Compound No. 2), 14.2 g of methyl iodide (0.1 mole), 50 ml of dimethylformamide and 2.76 g (0.02 mole) of anhydrous potassium carbonate and the reaction mixture was heated at 70 ° C. for 15 hours The solvent is then removed by distillation under partial vacuum (10 millibars) and the mixture is taken up with 100 ml of water and 2 × ml of CH 2 C 12. The aqueous phase is collected and then

  dried over sodium sulphate After distillation of the solvent in vacuo, 8 g of an oil are obtained which is chromatographed on silica (eluent: diisopropyl ether).

  There is thus obtained 5.1 g of compound No. 4 A, of formula:

N -N CH 3

CF.3 04 = N

2

  Yield: 63% Melting point: 90-92 ° C and 0.5 g of the compound N O 4 B of formula:

// N N

N N

melting at 148 C.

  According to another method of preparation, the compound NO 4 A could also be obtained by nitration of 2-methyl-1- (2-chloro-4-trifluoromethyl-phenoxy) -3-phenyl-5-tetrazole (melting point: 801 C Yield 72%). ), the latter compound having itself been obtained by alkylation of t (2-chloro-4-trifluoromethyl-phenoxy) -5-phenyl-tetrazole whose

  preparation is described in Example 1.

  EXAMPLE 5 Preparation of 2-methyl-2-nitro-2 (2,4-dichlorophenyl) -5-phenyltetrazole (Compound No. 5) 5.4 g (0.024 mole) of methyl are introduced into a 1000 ml three-necked flask. 2- (5-nitro-5-fluoro-phenyl) -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. The reaction mixture is stirred for 30 minutes at room temperature and then heated at 800 ° C. for 7 hours. The mixture is allowed to cool and then the solvent is evaporated off under vacuum. An oil is obtained which is taken up in 150 ml of water.

  CH 2 C 12, then washed with 3 x 50 ml of H 2 O and decanted After drying over Na 2 SO 4, filtered and evaporated to give a yellow oil which is crystallizes in a 50/50 diisopropyl ether / hexane mixture.

  After filtration, rinsing with 2 × 15 ml of diisopropyl ether, drying and drying in air, 5.8 g of the desired compound of formula (compound No. 5) are obtained.

N -N CH 3

ci C 1 C

C 1 2

  Melting point: 1151 C. Yield: 66% The 2-methyl-2- (2-nitro-5-fluoro-phenyl) -tetrazole used as starting material was prepared by alkylation of 5-nitro-5-fluoro-phenyl-tetrazole. in acetone, using CH 3 I, in the presence of K 2 CO 3 (5-nitro-5-fluoro-phenyl) -tetrazole was itself prepared by nitration, (3-fluorophenyl) -5 tetrazole using nitric acid

Example 6

  By operating according to the method of Example 4 from the appropriate raw materials, the following compounds were prepared: 2-ethyl-1-nitro-2 (2-chloro-4-trifluoromethylphenoxy) -5-phenyl-5-tetrazole (compound n 6) Yield: 45% Melting point: 66-67 C-2-isopropyl-2-nitro-2- (2-chloro-4-trifluoromethylphenoxy) -5-phenyltetrazole (Compound No. 7) Yield: 37% Ethoxycarbonylmethyl-2-nitro oil 2- (2-chloro-4-trifluoromethyl-phenoxy) -5-phenyl-tetrazole (Compound No. 8) Yield: 50% Melting point: 127 ° C. (1-ethoxycarbonylethyl) -2-nitro-2 (2-chloro-trifluoromethyl) Phenoxy-5-phenyl-5-tetrazole (Compound No. 9) Yield: 65% Melting point: 132 C 2-ethoxycarbonyl-2-nitro-2 (2-chloro-4-trifluoromethylphenoxy) -5-phenyl-5-tetrazole (Compound No. 10) Yield: 95% Melting point: 140 ° C The following examples, Nos. I, II and III illustrate

  the herbicidal properties of the compounds according to the invention.

  EXAMPLE I Herbicidal Activity in a Greenhouse, in Collection of Plant Species An aqueous suspension is prepared having the following composition: active ingredient to be tested 40 mg, Tween 80 50 mg, distilled water containing 1 per 1000 weight of Scurol O qs 40 ml , grinding the active ingredient in a Potter mill and then suspending it in water containing the Tween

and Scurol 0.

  Tween 80 is a wetting agent consisting of

  polyoxyethylenated sorbitan monolaurate.

  Scurol O is a surfactant composed of polyoxyethylated alkylphenols, mainly octylphenol

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  polyoxyethylated with 10 moles of ethylene oxide.

  The aqueous suspension described above is then, if necessary, diluted with distilled water containing 1 per 1000 Scurol 0, so as to obtain the desired concentration.

  Pots 6.5 cm in diameter and 8 cm in height are used, half of which contain clay-silty earth.

  and half of the river sand.

  In each pot, we sow 30 seeds of one of the following 10 plant species: wheat (Triticum sativum), variety Caton TRIT Vulpin (Alopecurus myosuroides) ALOP Wild oat (Avena fatua) AVEN lentil (Lens culinaris), broad blond variety , LENS Radish (Raphanus sativus), variety Round pink with white tip e RAPHI Vegetable beet (Beta vulgaris), variety Cerès ** BETA Lettuce (Lactuca sativa), golden yellow goose variety MILK Buckwheat (Polygonum fagopyrum) FAG Amaranth (Amarantus) caudatus) AMA The preemergence treatment is carried out by spraying on the seeded surface the aqueous suspension of the

  active ingredient, at the desired concentration, each pot receiving about 0.3 ml of the aqueous suspension.

  After treatment, let the surface dry and then cover the seeds with a layer of soil

about 2 mm thick.

  Twice daily, the pots are sprinkled with water and kept in the greenhouse at a temperature of 22 ° to 24 ° C., at a relative humidity of 70 to 80%, under artificial lighting providing about

  5.0001 ux at the plant level, for 16 consecutive hours per 24 hours.

  Twenty-one days after the treatment, the number and height of the living plants in the pots treated with the active ingredient tested and also the number and height of the same plants in the control pots which have been treated under the same conditions are noted. , without active ingredient. The percentage reduction in number N%, calculated as follows: number of live plants in the treated pots N% = x 100 number of live plants in the control pots the percentage reduction in height H% calculated as follows: average height of living plants in treated pots E% at x 100 mean height of live plants in the control pots From N% and H%, the PERCENTAGE IN RELATION TO THE WITNESS is calculated, equal to: N% x H%

  The values thus obtained are recorded in the table (I) located at the end of the description.

  table, a value equal to O means a complete herbicidal activity and a value equal to 100 means the absence

total herbicidal activity.

  EXAMPLE II Herbicidal activity in a greenhouse, post-emergence of the plant species The procedure is as described in Example I, but with the following differences: after sowing the seeds, they are covered with a 5 mm layer of soil of approximately thickness, the pots are placed in the greenhouse and the seeds are allowed to germinate so as to obtain seedlings at the desired stage of development, the treatment with the compounds according to the invention is carried out when the plants are at next stage: stage 2 to 3 leaves for wheat, foxtail, lettuce and amaranth, at stage 3 true leaves for lentils ,. stage 2 well-developed cotyledonary leaves for buckwheat, beetroot and radish; According to this post-emergence treatment (or post-emergence according to an equivalent denomination), the solution or suspension containing the active ingredient is sprayed on

  the plant and let the plants dry.

  As in the case of the previous example, the results are observed twenty-one days after the treatment and the percentage is thus determined with respect to

  control according to the method described in the previous example.

  The values thus determined are recorded in

  Table II at the end of the description.

  EXAMPLE III Herbicidal Activity and Selectivity with Respect to Greenhouse Cultures, Post-emergence of Plant Species The procedure described in Example II is carried out using the following plants: Rice Crops (Oryza sativa) Wheat (Triticum) vulgare) Weevils Vulpin (Alopecurus myosuroïdes) Panisse (Echinochloa crus-galli) 30 Setaria (Setaria viridis) Velvet (Abutilon theophrasti) Hard grass (Sida spinosa) Annual chrysanthemum (Chrysanthemum annuum) Matricaria (Matricaria matricarioïdes) 35 Veronica of Persia (Veronica persica) ) Plantain (Plantago lanceolata) Amaranth Fox tail (Amarantus caudatus) Black nightshade (Solanum nigrum) White mustard (Sinapis alba) Bindweed (Convolvulus arvensis) Stellaria (Stellaria media). The percentages relative to the control are determined according to the method described in Example II The values

  thus determined are given in Table III at the end of the description.

  The results described in Examples I, II and III demonstrate the good herbicidal activity of the compounds according to the invention as well as the selectivity of compound No. 8 with respect to rice and wheat, at the dose of 0, 5 kg / ha For their practical use, the compounds according to the invention are generally used in the form of

  compositions also included within the scope of the present invention.

  These compositions usually comprise, in addition to the active ingredient (compound of formula I), one or

  several supports (or diluents), solid or liquid, acceptable in agriculture and one or more surfactants also acceptable in agriculture If necessary, they may contain moreover various additives equally acceptable in agriculture.

  Usually these compositions comprise from about 0.05% to 99% by weight of active ingredient, about

  0.01% to 20% by weight of one or more surfactants and from about 1% to 99.95% by weight of one or more liquid or solid carriers (or diluents).

  As solid supports, it is possible to use natural or synthetic silicas such as, for example, diatomaceous earth; natural or synthetic clays and silicates such as, for example, talc, attapulgite, vermiculite, kaolinites, montmorillonite, calcium and aluminum silicates; calcium carbonates; natural or synthetic resins such as polyvinyl chloride etc. As liquid carriers, water can be used alcohols such as, for example, isopropanol and glycols; ketones such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers; aromatic or araliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum fractions for example kerosene, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene, etc. When the carrier is water or a As the conventional organic solvent, the compositions according to the invention advantageously comprise, in addition to the active ingredient, a surfactant or other active ingredient with herbicidal properties. The surfactant may be an emulsifying, dispersing, deflocculating or wetting agent, of ionic type

or nonionic type. As surface-active agents, it is advantageous to use

  polycondensates of ethylene oxide with fatty acids or with fatty alcohols or with substituted phenols (especially with alkyl phenols or with aryl phenols) or with fatty amides, or with fatty amines. advantageously use fatty acid esters and sorbitan, sucrose derivatives, alkali metal or alkaline earth metal salts of lignosulfonic acids, alkylarysulphonic acids; salts of sulfosuccinic acid esters; phosphoric esters of polyoxyethylated alcohols or phenols; alkylbetaines or sulfobetaines, etc. The work w Mc Cutcheon's Detergents and Emulsifiers 1975 Annual "MC Publ Corp. Ridgewood, New Jersey USA

  describes many surfactants and gives recommendations for their use.

  U.S. Patent No. 3,713,804 discloses numerous anionic surfactants or

  cationic or nonionic acids that can be used in agriculture.

  The surfactant to be used in the compositions according to the invention may advantageously be chosen by those skilled in the art from the compounds or families of compounds described in these two documents. In addition to the active ingredient, the carrier and the surfactant, the compositions according to the invention may contain other additives such as non-surfactant dispersing agents, peptizers, protective colloids, thickeners, adhesives which increase the resistance to rain, stabilizers, preservatives, corrosion inhibitors, dyes, sequestering agents, defoamers, anti-foaming agents, anti-gels etc. The compositions according to the invention can be

  in quite diverse forms, solid or liquid.

  As forms of solid compositions, mention may be made of dusting powders (with an active matter content of up to 100%) and granules and microgranules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support by granulation from a powder (the content of active material in these granules being between 1 and 80% for the latter cases). These solid forms are generally used dry, without subsequent dilution. As forms of liquid compositions, or intended to constitute liquid compositions during application, mention may be made of wettable powders (or powders to be sprayed), emulsifiable solutions or concentrates, concentrated (or flowable) suspensions, solutions, particularly soluble concentrates in water,

emulsions and dispersions.

  Dusting powders usually contain from 0.1% to 5% by weight of active material, an inert carrier which may be an impregnating carrier such as

  silica and, when necessary, from 0 to 10% by weight of one or more stabilizers and / or other additives such as penetrants, adhesives, anti-caking agents or dyes. They are usually prepared by premixing the active material with the inert carrier and the mixture is then milled in a mill.

  Granules and microparticles, generally as active ingredients, may be pre-manufactured and subsequently impregnated or mass-produced, for example by spraying or by extrusion. In the latter case, they require the addition of binders and products. The surfactants for their fast disintegration on the ground contain, in general, from 0.5 to 10% by weight of active material, from 0 to 10% by weight of additives such as stabilizers, slow release modifying agents, of the

binders and solvents.

  Wettable powders (or powder spray) are usually prepared to contain from 20 to 95% active ingredient, and usually contain, in addition to the solid support, 5% OA of a wetting agent, 3 A 10% of a dispersing agent, and, when necessary, 10% OA of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, colourants, etc. By way of example, here is a composition of a wettable powder A 50% active ingredient 50% sodium lignosulfonate 5% sodium dibutylnaphthalene sulfonate 1% clay (kaolin) 44% Another example of wettable powder has the following composition: active ingredient 50% sodium and / or calcium lignosulfonate (deflocculant) 5% isopropylnaphthalene sulfonate (anionic wetting agent) 1% anti-caking silica 5% kaolin (filler) 39% To obtain these powders or wettable powders, theThe active ingredient in suitable mixers with the additional substances is milled with suitable mills or other mills. Thus, sprayable powders whose wettability and suspension are advantageous can be suspended in water with water. any desired concentration and this suspension can be used very advantageously especially for application to the leaves of plants The emulsifiable solutions or concentrates contain the active ingredient dissolved in a solvent (generally an aromatic hydrocarbon) and in addition, when necessary, an auxiliary solvent or cosolvent which may be a ketone, an ester, an ether-oxide, etc. In general, they contain from 5 to 60% by weight / volume of active ingredients, from 2 to 20% by weight / volume of emulsifying agent and can be prepared, for example, by dissolving active material, in the solvent or in the mixture of solvents and emulators sifiants,

  in a tank equipped with good agitation and a flow of fluid for heating or cooling.

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

  Concentrated (or "flowable") suspensions consist of a suspension of fine solid particles of the active ingredient in water or a non-solvating oil, prepared so as to obtain a stable fluid product, not settling. They usually contain from 10 to 50% by weight of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives and, as a carrier, water or an organic liquid in which the active ingredient has little or no solubility: certain organic solids or inorganic salts may be dissolved in the holder for

  assist in pocketing sedimentation or as antifreeze for water.

  These concentrated suspensions are prepared by very finely grinding the active material, then dispersing the active material in the liquid carrier containing the auxiliary ingredients, and then the dispersion obtained is milled in a ball mill. From concentrated suspensions, it is possible to obtain dilution with water of

  suspensions of any desired concentration.

  These aqueous suspensions or emulsions of the active material described above, for example the compositions obtained by diluting with water a wettable powder, or an emulsifiable concentrate, or a concentrated suspension, are included in the general scope of the compositions according to the invention. The emulsions may be of the water-in-water or oil-in-water type and may have a consistency.

  thick like that of a "mayonnaise".

  Finally, the present invention relates to a method for the selective weeding of crops, in particular rice and wheat crops. This process is characterized in that it consists in applying to the soil, taken from said cultures, an effective amount with respect to weeds, but not phytotoxic to the cultures of a compound according to formula (I) The amount of active ingredient to be used may vary according to the compound used the type of crops the climatic conditions, the nature of the weeds to destroy.

TABLE (I)

  Herbicide activity in greenhouse at harvest Percentage compared to controls: Identical to control No herbicide activity 0: Total herbicidal activity

PLANT

TRIT ALOP AVEN LENS RAP He

32 36 55 85 100

29 75 29 7

34 O il 35 26

14 76 100 90

83 32 66 41 100

63 90 100 5

  TABLIEAU Il Herbicidal activity is postemergence-controlled Percentage compared with controls

  X: identical to the control no herbicide activity%: total herbicidal activity.

PLANT

  _, Co.pos A Dose TRIT ALOP AVEN LENS RAPH BETA LACT AMA FAG kg / ha

I 10 100 100 100 75 O 57 100

2 I 64 56 73 32 O 10 O O

4 A 2.2 39 O 22 17 O O O O

6 1 77 10 73 8 9 3 4 O

7 1 100 34 80 67 25 16 O 6

8 1 83 75 83 8 O O 2 O _

TABLE III

  Herbicide Activity in Postemergence Greenhouse Percentages Compared to Controls: Same as Control No Herbicide Activity

0: total herbicidal activity.

Compound

NO 3 NI 4 TO NI 8

  Dose Kg / ha 0.5 0.5 0.5 Oryza sativa 54 88 Triticum vulgare 100 61 85 Alopecurus myosuroides 13 67 Echinochloa crus-galli 34 46 Setaria viridis 96 O 15 Abutilon theophrasti 50 O 47 Sida spinosa 20 20 Chrysanthemum annuum 23 8 O Matricaria matricarioldes 15 Veronica persica 0 0 Plantago lanceolata O 4 Amarantus Caudatus "00 Solanum nigrum 8 OO Sinapis alba OO Convolvulus arvensis O 3 Stellaria media 7 54 Society known as: RHONE-POULENC AGROCHIMIE

Claims (3)

  1) Derivative of phenoxybenzoic acid, characterized in that it corresponds to general formula (I): 0 'N 8 N _N <1)   wherein: X represents a halogen atom, or a lower alkyl radical, substituted by one or more halogen atoms, Y represents a hydrogen or halogen atom, or a CF 3, CN, NO 2 radical; or CH 3, ZD represents the nitrogen atom or the radical -C = in which Z represents a hydrogen or halogen atom, W represents a hydrogen or halogen atom or the nitro radical, R represents the hydrogen atom or a halogen atom, or a radical chosen from the radicals: optionally substituted alkyl; optionally substituted aryl; lower alkenyl; lower alkynyl; optionally substituted lower alkylthio; optionally substituted amino; CO-R 'wherein R' represents a substituent; In which R "represents a substituent; -OH and -CN;   and agriculturally acceptable salt thereof.   2) Compound according to claim 1, characterized in that it corresponds to the formula (I) in which: X represents the trifluoromethyl radical, Y represents the chlorine atom, D represents the radical -CH =, W represents the nitro radical, and R represents an alkyl radical, optionally substituted. 3) Process for the preparation of a compound according to claim 1), characterized in that it consists in reacting the phenyltetrazole of formula (II) N-N A W   in which W and R have the same meaning as in claim 1) and A represents the hydroxyl radical or a halogen atom, on the compound of formula (III) B (III)   wherein X, Y, D have the same meaning as in claim 1) and B represents a halogen atom or the hydroxy radical, it being understood that B is chosen to be different from A. 4) Process for the preparation of a compound having the formula (I) ON N Y C -4 R X O N (I)   in which W represents a halogen atom and X, Y, D and R have the same meaning as in claim 1), characterized in that it consists in halogenating a compound of formula (IV) @ / N _N N 4 XN == N (IV)   wherein X, Y, D and Z have the same meaning as before. A process for the preparation of a compound having the formula (I): ## STR1 ## wherein W represents the radical NO 2 and X, Y, D and R have the same meaning as in claim 1), characterized in that it consists of nitrating a compound of formula (IV): 25 / NN Y C 4 R (IV)   wherein X, Y, D and R have the same meaning as above. 6) Process for preparing a compound of formula (VII) 35 NNL X-CO O \ N = = (VII) S X O O O   in which X, Y and D have the same meaning as in claim 1), characterized in that it consists in reacting Na N 3 with the nitrile of formula (VI): Y / CN O (VI)   wherein X, Y, and D have the same meaning as before. 7) Process for the preparation of a salt of the compound of the formula (7) wherein X, Y, D and W have the same meaning as in claim 1), characterized in that it is necessary to react this compound of formula (IX) with a appropriate basis.   8) Process for preparing a compound of formula (I) N ,, - N Y C + R (I)   where X has the same meaning as in claim 1, except that it does not represent the hydrogen atom, and X, Y, D and W have the same meaning as in 1), characterized in that it consists in reacting a compound of formula (VIII) R T (VIII)   in which R has the same meaning as above and T represents a leaving group on the compound of formula (VII) JN N _ Y X \ \ = N C (VII)   wherein X, Y, D and W have the same meaning as before. 9) A herbicidal composition characterized in that it contains as active ingredient at least one compound according to one of claims 1 and 2).   Composition according to claim 9, characterized in that, in addition to the active ingredient, it comprises one or more agriculturally acceptable solid or liquid carriers and one or more surfactants. acceptable in agriculture.