LU85477A1 - NOVEL ARYLOXYBENZOIC ACID DERIVATIVES AND THEIR USE AS HERBICIDES - Google Patents

Description

The invention relates to new herbicidal compounds with a tetrazole group, derived from aryloxybenzoic acids. It further relates to the preparation of these new compounds as well as the compositions for agricultural use containing them.

2-nitro-5- [2'-chloro-4 '- (tr ifluoromethyl) phenoxy] benzoic acid, also known as acifluorfen and its salts, is known, as well as their use as herbicides, in particular for weeding soybeans. In the present description, the chemical compounds are designated by their name according to the French nomenclature but, in accordance with the Anglo-Saxon nomenclature, the numbers designating the position of the substituents have been placed before. the substitute and not after according to the French nomenclature.

In addition, numerous derivatives of acifluorfen have already been proposed, in particular alkyl, cycloalkyl, thioalkyl and phenyl esters, as well as mono or dialkylated amides. Such compounds are described by US patents US 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 present invention relates to derivatives of aryloxybenzoic acids, different from those described in the prior art and having excellent herbicidal activity.

. The new products according to the invention are characterized in that they correspond to the general formula U): 30

/ "- JL R

^ - / C \ N = i = N (I) xO- ° - (o) - "35 *> 2> in which s X represents a halogen atom, or a lower alkyl radical substituted by one or more d atoms 1 halogen, »5 Y represents a hydrogen or halogen atom, or a CF3, CN, NO2 or CH ^ radical, D represents the nitrogen atom or the radical -C (Z) = 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 aliphatic or aromatic or alkylthio or amino or acyl or .alkylsulfonyl or arylsulfonyl or hydroxy or cyano, these various radicals being optionally substituted; as' possible substituent, the following atoms or radicals may be mentioned: halogen, alkoxyalkoxy, alkoxy, hydroxy, lower alkyl or acyl, carboxyl, salts and esters (carboxylates) of this carboxyl group such as, for example, lower alkoxycarbonyls;

More particularly R can take one or other of the following meanings: alkyl optionally substituted, for example lower alkyl substituted or not by one or more of the abovementioned atoms or radicals; ’- aryl optionally substituted, for example by substituents similar to those mentioned above; - lower alkenyl; - lower alkynyl; - lower alkylthio optionally substituted, for example by one or more halogen atoms; - amino optionally substituted, for example by one or more lower alkyl radicals, or by an acyl radical; > 3 - CO-R 'in which R' represents a substituent, for example the OH radical or a lower alkoxy radical or an aryloxy radical, or the amino radical itself optionally substituted; 5 - SO2-Rm in which R "represents a substituent, such as, for example an alkyl or aryl radical; - or a radical -OH or -CN.

For the purposes of this text, the adjective "lower", when it qualifies a radical, means that this radical 10 contains at most 6 carbon atoms.

The dotted lines in formula (1) indicate the existence of a tautomerism.

The compounds according to formula (I) for which R 1 represents the hydrogen atom, have an acid character and can therefore form, with suitable bases *, salts which are acceptable in agriculture. These salts can also be used as herbicides and are therefore also included in the context of the invention. As an example of such salts, there may be mentioned salts of metals preferably of alkali metals such as sodium, potassium or lithium, or of alkaline earth metals such as calcium or magnesium, or ammonium salts or ammonium salts mono or polysubstituted such as isopropylammonium; triethanolammonium, morpholinium, etc ...

Depending on the position of the substituent R on the “tetrazole” cycle, the compounds according to formula (I) can exist in two isomeric forms (IA) and (IB) which are “i 4 also included within the scope of the invention, and in which the various substituents have the same meaning as in formula (I)

5 —N-R

<Y / - / C \ N = rN <IA) 10

/ sK - N

V / He

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 atom of chlorine D represents the radical -CH = 25 W represents the nitro group R represents an alkyl radical optionally substituted (for example by a lower alkoxycarbonyl radical).

; The invention also relates to the preparation of the compounds according to formula (I) and of the salts, usable in agriculture, of these compounds.

* 4 5

The compounds according to formula (I) can be prepared by the action of the phenyltetrazole of formula (II) y /; i

.C -4- R

5 .— / ^ N ^ N

a- ^ Q / -W (II) 10 in which W and R have the same meaning as in formula (I) and A represents the hydroxyl radical or a halogen atom (preferably fluorine or chlorine), on the compound of formula (III) 15 ^ Y: '* - @ - B UI11 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, that is to say that B represents a halogen atom when A represents the hydroxy radical and that B represents the hydroxy radical when A represents the atom halogen.

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), preference is given to starting materials. a phenyltetrazole (II) in which A represents the hydroxy radical and a compound (III) in which 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 35 substituents or symbols having the same meaning as in formula (I), preferably chosen as * i 6 starting materials a phenyltetrazole (II) in which A represents the halogen atom and a compound (III) in which B represents the hydroxy radical.

The reaction between phenyltetrazole (II) and compound (III) is generally carried out in the presence of a basic agent, at a temperature between 80 and 180 ° C; approximately, in a polar aprotic solvent, such as, for example, diraethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrroiidone, acetonitrile, acetone or in other equivalent polar aprotic solvents.

As basic agent, it is advantageous to use sodium or potassium hydroxides or carbonates. It is also possible to use the compounds of formula (II) or (III) & "hydroxy group in the form of an alkali phenate s previously formed.

The phenyltetrazole of formula (II), used as starting material can be prepared by the action of NaN3 on a nitrile of formula (V)

20 _ CN

A- <§> - "(V, in which A and W have the same meaning as in formula (II), provided that when W represents the nitro radical, A necessarily represents a halogen atom. This reaction s 'performs according to the method; described by K. Kadaba in Synthesis - 1973 - p. 71-84.

The phenyltetrazole corresponding to formula (II) is thus obtained in which A and W have the same meaning as above and R represents the hydrogen atom.

The phenyltetrazoles according to formula (II) for which R represents a substituent other than the hydrogen atom 7 4 * *> can be prepared from the phenyltetrazole obtained previously, by the action of a reagent of formula (VIII) 5 R - T (VIII) in which R has the same meaning as above and T represents a leaving reactive group such as for example a halogen atom (preferably the iodine or bromine atom) or an arylsulfonic radical such as the benzene sulfonyloxy, toluene sulfonyloxy, xylene sulfonyloxy radicals.

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 compound according to formula (I) for which W represents the hydrogen atom, and which corresponds to S the following formula (IV): 20

κ, Ν-N

y / -3- · 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 usual 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 by operating at low temperature (between -20 ° C. and + 20 ° C.).

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

. 5 The compounds according to formula (I) for which W

and R represent the hydrogen atom, the other * substituents and symbols having the same meaning as in formula (I) can also be prepared by the action of NaN ^ on a nitrile of formula (VI): 10

_y Y / CN

X "C / 1 (VI» 15. In which X, Y and D have the same meaning as in formula (I), operating according to the method of K. Kadaba described above. The compounds corresponding to the formula (VII): 20

Y C “Π— H

<VII> 25 in which the various symbols and substituents have the same meaning as above.

The compounds according to formula (I), for which R

30 represents a substituent other than the hydrogen atom, can also be prepared from the compounds according to formula (Vil), the preparation of which is described above, by action on this compound of a reagent of formula (VIII) 35 R - T (VIII), * 9 in which R and T have the abovementioned meanings.

The reaction is generally carried out in an inert organic solvent medium, at a temperature of the order of approximately 5 ° C. to 150 ° C.

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 compounds using an appropriate base, preferably sodium hydroxide.

At the end of the operation, according to one or other of the methods 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. 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 else chromatography in liquid phase or in vapor phase.

The following examples illustrate the invention without, however, limiting it. The structure of the compounds described in these examples was characterized by infrared spectrometry, by nuclear magnetic resonance spectrometry (R.M.N.) and by elemental analysis.

25 Example .1: Preparation of 5-13 '- (2 "-chloro-4" -tr ifluoromethylphenoxy) phenyl) tetrazole (compound ηβ 1)

0.15 1 of methanol is introduced into a three-liter three-necked flask, then 13.2 g of potassium hydroxide = 30 in pellets are added per portion, then, in one go, 18 g, or 0.1 mole of 5- (3'-hydroxyphenyl) tetrazole (crystallized with 1 mole of water), while keeping the temperature below 30 ° C. The whole is kept at this temperature for about half an hour and the solvent is distilled under an absolute pressure reduced to about 1 millibar. There is thus obtained, in the form of a brown oil, the potassium salt of 5- (31-hydroxyphenyl) tetrazole.

This brown oil is then dissolved in 100 ml of dimethyl sulfoxide and the solution 21.5 g (0.1 mole) of 3,4-dichloro (trifluoromethyl) benzene is added to the solution and the reaction mixture is heated at 130 ° C for 5 hours, then the temperature is allowed to return to ambient temperature (approximately 25 ° C.). The reaction mixture is then poured into 500 ml of water. The aqueous phase is extracted with 2 x 100 ml of methylene chloride. The aqueous phase is then collected which is acidified to pH = 1 with concentrated aqueous HCl. The formation of crystals consisting of unreacted tetrazole and an oil was observed, which was dissolved in 200 ml of methylene chloride. The organic phase obtained is washed several times with water and then dried over sodium sulfate. 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 then dried in an oven and finally recrystallized from a 50/50 mixture of water + ethanol.

This gives 13.2 g of compound 1 of formula:

N - N

/ 1

25 Cl, C -i | - H

Yield: 38% 30 Melting point: 173 ° C.

The 5- (3-hydroxyphenyl) tetrazole used as starting material was prepared by the action of NaN 3 on * cyano-3 phenol, in dimethylformamide, in the presence of ammonium chloride according to a method analogous to that described in Synthesis, 1973 - p. 71 S 84.

»V

11

The compound ηβ 1 was also obtained according to a second process described below:

17.6 g (0.059 r3 mole) of 5 3- (2'-chloro-4'-trifluoromethylphenoxy) benzonitrile are loaded into a three-necked flask; 4.2 g (0.065 mole) NaN ^; 3.4 g (0.065 mole) of ammonium chloride and 30 ml of dimethylformamide. The reaction mixture is brought to 100 ° C. for 4 h., It is allowed to return to ambient temperature and it is poured into 500 ml of water. A solution is obtained to which 6N HCl is added until pH * 1 and the mixture is stirred for 10 min. A white precipitate is formed which is filtered and then wrung with water. After wringing, air drying, 19.5 g of compound 1 are obtained.

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

EjxemBl.e _.- 2: Preparation of 5- [2'-nitro-5 '- (2 "-chloro-4" -tr ifluoromethylphenoxy) phenyl] tetrazole (compound n ° 2).

In 40 ml of concentrated sulfuric acid, 9.2 g (0.027 mol) of compound No. 1 are dissolved, and 40 ml of 1,2-dichloroethane are added to the solution thus 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, then the mixture is kept 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 x 100 ml of dichloromethane, the organic phase is dried, then the solvent is removed by distillation. 12 g are obtained 8 g (78% yield) of an 80/20 mixture of s * 5- [2'-nitro-5 '- (2 "-chloro-4" -tr ifluoromethylphenoxy) phenyl] - tetrazole and 5 - [2'-nitro-3 '- (2 "-chloro-4" -tr ifluorornethylphenoxy) phenyl] -5 tetrazole.

By chromatography on silica (eluent s ethanol / CH2Cl2 / acetic acid in respective volume proportions 1.5 / 15 / 0.1, 4.2 g of the desired compound (compound no. 2) of formula s 10 are obtained

N - N

y C1 _Æ 4— H

__ / r \\ / TA nn —- n CF3 \ Q / 0 \ 0 ^ “N02 15. Yield: 47%

Melting point: 142 ° C.

and 0.4 g of 5 “[2'-nitro-3 '- (2" -chloro-4 "-tri f luor adorned thylphenoxy) phenyl] tetrazole, melting at 206 ° C.

Example 3; Preparation of the sodium salt of compound 2.

This salt is compound n ° 3.

1.16 g of compound 2 are dissolved in 10 ml of water and an equivalent of IN sodium hydroxide.

25 The water is removed by vacuum distillation S

60 ° C and thus 0.9 g of the desired compound is obtained, in the form of a yellow solid, of formula: r ν_νΊθ 30 / / C1 / C \ · * o -3 - <^ o ^ HOrN Na 35 Yield : 75%

Melting point above 250 ° C

13

Example 4 Preparation of 2-methyl-5- [2'-nitro-5 '- (2 "-chloro-4" -tr ifluoromethylphenoxy) phlnyl] tetrazole (compound ηβ 4A) and l-methyl-5- [2 '-nitro-5' - (2 "-chloro-4" -trifluoromethylphenoxy) phenyl] tetrazole (compound No. 4B).

7.72 g (0.02 mole) of compound 2, 14.2 g of methyl iodide (0.1 mole), 50 ml of dimethylformamide and 2.76 are loaded into a 250 ml three-necked flask g (0.02 mole) of anhydrous potassium carbonate and the reaction mixture is 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 x 100 ml of CH2Cl2. The organic phase is collected and then dried over sodium sulfate. After distilling off the solvent in vacuo, 8 g of an oil are obtained which is chromatographed on silica (eluent diisopropyl ether).

5.1 g of compound No. 4A are thus obtained, of formula: N - N- CH ·, ✓ I 3 20 / Cl, c]

/ ^ A N = N

CF3- \ O / - ° - \ O) u02

Efficiency: 63%

25 Melting point: 90-92eC

and 0.5 g of compound No. 4B of formula:

Cl c II

30 CF3 - <^ 0 - (^ t, 02SCH3 fondant I 148 ° C.

14

According to another mode of preparation, compound No. 4A could also be obtained by nitration of 2-methyl-5- [3 '- (2 "-chloro-4" -1r ifluoromethyphenoxy) phenyl] tetrazole (melting point : 80eC - Yield 72.5%), the latter compound having itself been obtained by alkylation of the compound ηβ 1.

Example. 5, î Preparation of 2-methyl-5- [2'-nitro-5 '- (2' ', 4' '- dichlorophenyl) phenyl] tetrazole (compound No. 5).

10 5.4 g (0.024 mole) of 2-methyl-5- (2'-nitro-5'-fluorophenyl) tetrazole, 3.9 g (0.024 mole) of 2 are introduced into a 100 ml three-necked flask. 4-dichlorophenol, 3.3 g (0.024 mole) of potassium carbonate and 50 ml of dimethylformamide. The reaction mixture is stirred for 30 min at room temperature and then heated to 80 ° C. for 7. hours. It is allowed to cool and then the solvent is evaporated under vacuum. An oil is obtained which is taken up in 150 ml of CH 2 CH 3 "then washed 3 times with 50 ml of H 2 0 each time; we decant. After the organic phase has dried over Na2SO4, it is filtered and then evaporated to obtain a yellow oil which is crystallized from an equivolumic mixture of diisopropyl ether / hexane. After filtration, rinsing with 2 x 15 ml of diisopropyl ether, spin drying and air drying, 5.8 g of the desired compound 25, of formula (compound No. 5) N —N- CH3 / l cl, are obtained. 30 Cl- (Ç ^ ° - (C ^ 02

Melting point î 115eC Yield: 66% 35 15

The 2-methyl-5- (2'-nitro-5'-fluorophenyl) tetrazole used as starting material, was prepared by alkylation of (2-nitro-5-fluorophenyl) tetrazole, in acetone, using CH ^ I, in the presence of K2C03. The 5- (2-nitro-5-fluorophenyl) tetrazole was itself prepared by nitration of the 5- (3'-fluorophenyl) tetrazole using nitric acid.

By operating according to the method of Example 4 starting from the appropriate raw materials, the compounds Nos. 6 to 15 were prepared.

The various compounds obtained in the various examples 1 to 15, and the exception of compound No. 4B (a compound has the number of the example which corresponds to it) have the formula:

^ N_N_R

ci c | x- ^ Q ^ - · o ^ py w (x)

The meaning of the substituents X, W and R for the various compounds as well as the yield (RDT) of the example and the melting point of the product (or its spectral characteristics) are collated in Table (I). The compounds which have an asymmetric carbon * exist in two enantiomeric forms R or S. In this case, formula (X) [as well as formula (I)] must well be understood as defining one or the other of these two forms, or as defining the mixture of the two in either equivalent (racemate) or preponderant proportions for one or the other of them.

16

The following compounds can be prepared according to a process analogous to that of Example 4: 2- (methoxycarbonyl-ethyl) -5- [2'-nitro-5 '- (2 "-chlo-ro-4" -trifluoromethyl- phenoxy) phenyl] tetrazole 5 (R enantiomer), 2- (methoxycarbonyl-1 ethyl) -5-l2'-nitro-5 '- (2, l-chlo-ro-4 "-trif luorométhy]) phenoxy] tetrazole ( enantiomer S), 2- (methoxycarbonyl-1 ethyl) -5- [2'-nitro-5 '- (3M-chlo-ro-5 "-trifluoromethyl pyridyl-2" -oxy) phenyl] tetrazole 10 (racemate, as well than its R enantiomer and its S enantiomer).

The examples below, Nos. 16 to 20 illustrate the herbicidal properties of the compounds according to the invention. The terms pre-emergence and pre-emergence are synonymous; the terms post-emergence and post-emergence are synonymous.

Example .16 - Herbicidal activity in a greenhouse, pre-empting plant species.

An aqueous suspension is prepared having the following composition: 20 - active material to be tested .......... 40 mg, - Tween 80 .................. ....... 50 mg, - distilled water containing 1 per 1,000 by weight of Scurol 0 .......... qs 40 ml, by grinding the active material and then suspending it in water containing Tween 80 and Scurol 0.

. Tween 80 is a wetting agent consisting of polyoxyethylenated sorbitan monolaurate.

Scurol 0 is a surfactant consisting of polyoxyethylenated alkylphenols, mainly octylphenol polyoxyethylenated with 10 moles of ethylene oxide.

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

9 17

Pots with a diameter of 6.5 cm and a height of 8 cm are used, containing half of the clayey soil and half of the river sand.

In each pot, 30 seeds of one of the • 5 plant species below are sown: symbols

Wheat (Triticum sativum), variety Caton ... TRIT

Vulpin (Alopecurus myosuroides) ........ A LO P

Wild oats (Avena fatua) ............. AVEN

10 Lentil (Lens culinaris), Large variety

blonde .................................. LENS

Radish (Raphanus sativus), Round variety

pink & white tip ....................... RAPH

Vegetable beet (Beta vulgaris),

15 Cerës variety ........................... BETA

; Lettuce (Lactuca sativa), gotte variety

golden yellow .............................. LACT

Buckwheat (Polygonum fagopyrum) .......... FAG

Amaranth (Amaranthus caudatus) ........... AMA

The pre-emergence treatment is carried out by spraying the aqueous suspension of the active ingredient, at the desired concentration, onto the seeded surface, each pot receiving approximately 0.3 ml of the aqueous suspension.

After treatment, the seeded surface is left to dry and then the seeds are covered with a layer of soil of about 2 mm thick.

Twice a day, the pots are sprinkled by sprinkling and kept in the greenhouse at a temperature of 22 to 24 ° C, at a relative humidity of 70 30 I 80%, under artificial lighting bringing about 5000 lux to the plant level, for 16 consecutive hours per 24 hours.

Twenty-one days after the treatment, note the number and the height of the living plants in the pots 35 treated with the active ingredient tested and also the number 18 and the height of the same plants in the control pots which were treated according to the same conditions, without active ingredient.

* We thus determine: .5 - the percentage reduction in number N%, calculated as follows:. number of live plants in treated pots N% ---------------------------------------- ---------- X 100 number of living plants in control pots 10 - the percentage reduction in height H% calculated as follows: average height of living plants in treated pots H% = ---- --------------------------------------------- x 100 15 medium height living plants in the control pots from N% and H%, we calculate the PERCENTAGE IN RELATION TO THE WITNESS, equal to: NA Λ _H% 20 100

The values thus obtained are recorded in table (II). In this table, a value equal to 0 means complete herbicidal activity and a value equal to S 100 means the total absence of herbicidal activity.

plant species. B

We operate according to the method described in Example 16> with, however, the following differences: - after sowing the seeds, we cover them with a layer of soil about 5 mm thick, we place the pots in the greenhouse and the seeds are allowed to germinate so as to obtain seedlings at the desired stage of development *, 19 - the treatment using the compounds according to the invention is carried out when the plants are at the following stage: stage 2 S 3 leaves for wheat, vulpin, “5 lettuce and amaranth,. stage 3 true leaves for lentils,. stage 2 cotyledon leaves well developed for buckwheat, beetroot and radish; - according to this post-emergence treatment (or 10 post-emergence according to an equivalent name), the solution or suspension containing the active material is sprayed onto the plant and the plants are then left to dry.

As in the case of the previous example, the results are observed twenty-one days after the treatment and the percentage relative to the control is thus determined according to the method described in the previous example.

The values thus determined are recorded in table (III).

20 Example. 18 .Herbicide activity and selectivity vis-à-vis the crops,. In .. greenhouse, post-emergence. Of plant species

The operation is carried out according to the method described in Example 17, using the following plants: Rice (Oryza sativa)

Wheat (Triticum vulgare)

Vulpin (Alopecurus myosuroïdes)

Panisse (Echinochloa crus-galli) 30 Setaire (Setaria viridis)

Abutilon (Abutilon theophrasti)

Hard grass (Sidaspinosa)

Annual Chrysanthemum (Chrysanthemum annuum)

Hatricaria (Matricaria matricarioïdes) 35 Veronica of Persia (Veronica persica)

Plantain (Plantago lanceolata) 20

Amaranth fox tail (Amaranthus caudatus)

Black nightshade (Solanum nigrum)

White mustard (Sinapis alba)

Bindweed (Convolvulus arvensis) - 5 Stellar (Stellaria media).

The percentages are determined relative to the control according to the method described in Example 17. The values thus determined are indicated in Table (IV). Example ,,! 9 s 10 Application he.tbleide ,. ..extract, .species

In 9 x 9 x 9 cm pots filled with light agricultural soil, a number of seeds is sown according to the plant species and the size of the seed.

. The pots are treated by spraying with a mixture of quantity corresponding to a volume application rate of 500 l / ha and containing the active material at the desired concentration.

The treatment with the porridge is therefore carried out on seeds not covered with soil (the term porridge is used to denote, in general, the compositions diluted with water, such as they are applied to plants).

The porridge used for the treatment is one. aqueous suspension of the active ingredient containing 0.1% by weight of Cemulsol NP 10 (surfactant consisting of * polyethoxylated alkylphenol, in particular nonylphenolpolyethoxylate) and 0.04% by weight of tween 20 (surfactant consisting an oleate of a polyoxyethylene derivative of sorbitol).

This suspension was obtained by mixing and grinding the ingredients in a micronizer, so as to obtain an average particle size of less than 40 microns.

21

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

After treatment, the seeds are covered with a * 5 layer of soil about 3 mm thick.

The pots are then placed in tanks intended to receive the irrigation water, under sub-irrigation, and kept for 21 days at room temperature under 70% relative humidity.

10 After 21 days, the number of living plants in the pots treated with the spray containing the active ingredient to be tested is counted and the number of living plants in a control pot treated according to the same conditions, but using a spray. not containing active ingredient.

The percentage of destruction of the treated plants relative to the untreated control is thus determined. A percentage of destruction equal to 100% indicates that there has been complete destruction of the plant species considered and a percentage of 0% indicates that the number of living plants in the treated pot is identical to that in the control pot. The results obtained in this example 19 are presented in table (V).

Herbicide application., Postleyed species.

25 plants -. In 9 x 9 x 9 cm pots filled with light agricultural soil, a number of seeds is sown determined according to * the plant species and the size of the seed.

The seeds are then covered with a layer of soil about 3 mm thick and the seed is allowed to germinate until it gives birth to a seedling at the appropriate stage. The processing stage for grasses 22 is the "second leaf in formation" stage. The suitable stage for soybeans is the "first spreading trifoliate leaf" stage. The processing stage for other broadleaf weeds is the "spreading cotyledons, first true leaf developing" stage.

The pots are then treated by spraying with a mixture of quantity corresponding to a volume application rate of 500 l / ha and containing the active material at the desired concentration.

The slurry was prepared in the same manner as in Example 19.

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

The treated pots are then placed in tubs intended to receive the irrigation water, under sub-irrigation, and kept for 21 days at room temperature under 70% relative humidity.

After 21 days, the results are appreciated as indicated in Example 19. The results obtained in this Example 20 are presented in Table (V).

The plant species used in Examples 19 and 20 are grouped in Table (VI).

The products according to the invention generally have excellent antidecotyledonous activity in, taken, but especially post-emergent, from large soy weeds such as Abutilon, Ipomea or Xanthium.

* For their use in practice, the compounds according to the invention are generally used in the form of compositions also included in the context of the present invention.

These compositions usually comprise, in addition to the active material (compound of formula I), one or more supports (or diluents), solid or liquid, 23 acceptable in agriculture and one or more surfactants also acceptable in agriculture. If necessary, they can also contain various additives which are also acceptable in agriculture.

Usually these compositions comprise about 0.05% 99% by weight of active material, about 0.01% 20% by weight of one or more surfactants and about 1% 99.95% by weight of one or more carriers. (or diluents) liquids or solids.

As solid supports, use may be made of 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, etc ...; ethers; aromatic or arylaliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum fractions, for example kerosene, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene, etc.

When the support is water or a conventional organic solvent, the compositions according to the invention advantageously comprise, in addition to the active material, a surfactant.

The surfactant can be an emulsifying, dispersing, deflocculating or wetting agent, of ionic type or of nonionic type.

* '»24

As surfactants, polycondensates of ethylene oxide may advantageously be used with fatty acids or with fatty alcohols or with substituted phenols (in particular with alkyl phenols or i. 5 with aryl phenols) or with fatty amides, or with fatty amines. It is also advantageous to use fatty acid esters of sorbitan, sucrose derivatives, alkali or alkaline earth metal salts of lignosulfonic acids, of alkylarylsulfonic acids; Ester salts of sulfosuccinic acids; alkylbetaines or sulfobetaines, etc ...

"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 describes many anionic or cationic or nonionic surfactants for use in agriculture. The surfactant to be used in the compositions according to the invention can advantageously be chosen by a person skilled in the art from the compounds or families of compounds described in these two documents or elsewhere.

In addition to the active material, the support and the surfactant, the compositions according to the invention may contain other additives such as agents, non-surfactant dispersants, peptizers, protective colloids, thickeners, increasing adhesives. resistance to rain, stabilizers, preserving agents, corrosion inhibitors, dyes, sequestrants, anti-foaming agents, anti-caking agents, anti-freezing agents, etc.

The compositions according to the invention can be in fairly diverse forms, solid or liquid.

· »25

As forms of solid compositions, mention may be made of powders for dusting (with an active ingredient content of up to 100%) and granules and microgranules, in particular those obtained by extrusion, by compacting, by impregnation with a granulated support, by granulation from a powder (the content of active material in these granules being between 1 and 80% for these 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 spraying powders), solutions or concentrates. emulsifiable, concentrated (or flowable) suspensions, solutions, in particular water-soluble concentrates, emulsions and dispersions.

The dusting powders usually contain from 0.1 to 5% by weight of active material, an inert support, which can be an impregnation support such as silica, and, when necessary, from 0 to 10% by weight one or more stabilizers and / or other additives such as penetrating agents, adhesives, anti-caking agents or colorants. They are usually prepared by premixing the active ingredient with the inert carrier and the mixture is then ground in a mill.

The granules and micro-granules, generally with a low content of active material, can be prefabricated and then impregnated, or manufactured in the mass, for example by atomization or by extrusion. In the latter case, they require the addition of binders and surfactants to ensure their rapid disintegration on the ground. They generally contain from 0.5 to 10% by weight of active ingredient, from 0 to 10% by weight of additives such as stabilizers, slow release modifiers, binders and solvents.

26. {

Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0. 5 to 5% of a wetting agent, 3 to 10% of a dispersing agent, and, when necessary, from 0 to 10% of a or; several stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc.

10 As an example, here is a composition of a 50% wettable powder: - active ingredient ....................... 50% - 1ignosulfonate sodium ............. 5% - sodium dibutylnaphthalene sulfonate. 1% 15 - clay (kaolin) ...................... 44%

Another example of a wettable powder with the following composition: - active material ....................... 50% - sodium lignosulfonate and / or cal- 20 ci um (def loculant) ................... 5% - isopropylnaphthalene sulfonate (anionic wetting agent) ........... 1% - silica anti-caking .................. 5% - kaolin (filler) ....................... 39 % 25 To obtain these% pulverizing powders or wettable powders, the active ingredient is intimately mixed in appropriate mixers with the additional substances and ground with mills or other suitable grinders. Powders to be sprayed are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and this suspension "can be used very advantageously in particular for application to the leaves of plants.

35. s 27

The emulsifiable solutions or concentrates contain the active substance dissolved in a solvent (generally an aromatic hydrocarbon) and in addition, when necessary, an auxiliary or co-solvent 5 which may be a ketone, an ester, an ether-oxide, etc. ..

In general, they contain from 5 to 60% by weight / volume of active material, from 2 to 20% by weight / volume of emulsifying agent and can be prepared, for example, by dissolving the active material, in 10 solvent or in the mixture of solvents and emulsifiers, with good stirring and with heating or cooling.

From these solutions or concentrates. emulsifiable, emulsions of any desired concentration which can be obtained by dilution with water. ‘Are particularly suitable for the use of the compounds according to the invention.

The concentrated (or "flowable") suspensions consist of a suspension of fine solid particles of the active ingredient in water or a non-solvent oil, prepared so as to obtain a stable, non-depositing fluid product. They usually contain from 10 to 75% by weight of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10 25% of suitable additives such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the carrier to help prevent sedimentation or as antifreeze for water.

4 i 28

These concentrated suspensions are prepared by 9 * very fine grinding of the active material, then by dispersing the active material in the liquid support containing the auxiliary ingredients, then the dispersion obtained is ground in a ball mill. From concentrated suspensions, suspensions of any desired concentration can be obtained by dilution with water.

These aqueous suspensions or emulsions of the active ingredient described above, for example the compositions obtained by diluting with wettable powder, or an emulsifiable concentrate, or a concentrated suspension, are included in the general scope of the compositions according to 1 ' invention.

The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

The present invention finally relates to a process for selective weeding of crops, in particular of rice and wheat crops. This process is characterized in that it consists in applying to the soil, removed from said crops, an amount effective against weeds, but not phytotoxic towards crops of a compound according to the formula (I). The amount of active ingredient to be used may vary depending on the compound used, the type of crop, the climatic conditions, the nature of the weeds to be destroyed.

i t 29 TABLE (I)

CQMPO χ „RTD POINT OF CHARACTERISTICS

SE NO. K (%) FUSICN (° C) SPECTRAL IR

or NMR

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32 'Herbicide activity, in a greenhouse' in .postlevée

Percentages by ratio to controls 5 100: identical to control - no herbicidal activity 0: total herbicidal activity.

Compound n ° 3 n ° 4A n ° 8 10 Dose Kg / ha 0.5 0.5 0.5

Oryza sativa 54 88

Triticum vulgare 100 61 85

Myosuroid alopecurus 13 67 - 15 Echinochloa crus-galli 34 46

Setaria viridis 96 0 15

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Claims (17)

1. Products, usable in particular as herbicide, * 5 characterized in that they have the formula: / Æ-N y / 4- R (i) 10 "in which: X represents a halogen atom, or an alkyl radical 15, substituted by one or more halogen atoms, Y represents a hydrogen or halogen atom, or a radical CF ^ CNjNC ^ or CH3, D represents the nitrogen atom or the radical -C ( Z) = 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 an aliphatic or aromatic, alkylthio, amino, acyl, alkylsulfonyl, arylsulfonyl, hydroxy or, cyano radical, optionally substituted, as well as their acceptable salts in agriculture. 2. Products according to claim 1, characterized in that R is a radical substituted by one or more atoms or radicals such as halogen, alkoxy, hydroxy, lower acyl, carboxyl, carboxylate. 3. Products according to one of claims 1 or 2, characterized in that R represents the hydrogen atom or a halogen atom, or a radical chosen from t 36 radicals: optionally substituted alkyl; aryl ‘optionally substituted; lower alkenyl; lower alkynyl; optionally substituted lower alkylthio; optionally substituted amino; 4. Products according to one of claims 1) to 3) characterized in that: 15. is CF 3, A ï is Cl, D is -CH =, W is nitro or H, and R represents an alkyl radical, optionally 2o substituted. 5. Method for preparing a product according to one of claims 1 to 4, characterized in that it consists in reacting a phenyltetrazole of formula (II) 25 N - N #: i C -H— R (II) r- (v N— "* - (θ) -κ = 3o in which W and R have one of the meanings indicated in claims 1 to 4 and A represents the hydroxy radical or a halogen atom, with a compound of formula (III) 35 yyy— ((III) 6 * ♦ Γ 37 in which X, Y, D have one of the meanings indicated in the claim 1 and B represents a halogen atom or the hydroxy radical, it being understood that B is chosen to be different from A and that the hydroxylated reagent can be in phenate form. 5. CO-R 'in which R' represents a substituent such as the OH radical or a lower alkoxy radical or an aryloxy radical, or the amino radical itself optionally substituted; - SO ^ -R "in which R" represents a substituent such as aIkyle..ou aryle. -OH and -CN; and the agriculture acceptable salts of these compounds. 6. Process for the preparation of a product of formula (I) RY y C '* io / * _ / \ n ^ = nd) in which W represents a halogen atom and X, Y, 15 D and R have l 'one of the meanings indicated in the. Claims 1 to 4, characterized in that it consists in halogenating a compound of formula (IV) // ^ -? Y.e -Ü-K (IV) / - (J— / \ n ^ = n ° ~ Cy in which X, Y, D and R have one of the meanings given in claims 1 to 4. "7) Process for the preparation of a product of formula: ^ N—? Y -> - R Os in which X, Y, D and R have one of the meanings <38 indicated in claims 1) to 4), characterized in that it consists of nitrate a compound of formula (IV): ✓-JL R 5 __ / cnhJT 8. Process for the preparation of a product of formula (VII) 10 y, c -fl — H r ~ (r- (\ N = N <VII> X-Æ)> - 15 ΰ '£ in which X, Y and D have one of the meanings indicated in claims 1 to 4, characterized in that it consists in reacting NaN ^ with the nitrile 20 of formula (VI): / Y / CN 25 " 9. Process for the preparation of a product salt of formula (IX): 30: '"" in which X, Y, D and W have one of the meanings indicated in claim 1), characterized in that J * 39 that consists in reacting this compound of formula (IX) “with an appropriate base, preferably sodium hydroxide. 10. Process for the preparation of a compound of formula (I) B / Æ-N & '1 yc "3— R r- / f- / x_ @ ~ ° ^ 2rw 10 in which R, X, Y, D and W have one of the meanings indicated in claims 1 to 4 and R is other than the hydrogen atom, characterized in that it consists in reacting a compound of formula 15 (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) // 1— \ Si. C “Π— H (VII) / - (y- (N'Nr. ~ N 25 ΧΗ® · 0- \ 2) A 11. Herbicidal composition characterized in that it contains as active material at least one product according to one of claims 1 to 4. - 12) Composition according to claim 11, characterized in that, in addition to the active material, it comprises an a1 or more solid or liquid carriers acceptable in agriculture and one or more surfactants acceptable in agriculture. 40 13. Composition according to claim 12, characterized in that it comprises 0.5% 95% of active material. 14. Composition according to claim 13, characterized in that it comprises 1 I 95% of support and 0.1 to 20% 5 of surfactant. 15. Method for the selective weeding of crops, characterized in that an effective dose of an active material is applied according to one of claims 1 to 4. 10 16) Method according to claim 15, characterized in that a composition is applied according to one of claims 11 to 14, the active material being applied at a rate of 0.01 to 5 kg / ha, preferably 0.1 at 2 kg / ha. '15 17) Method according to one of claims 15 to 16, characterized in that the culture is soy. Λ ^ *