BE895815A - HETEROAROMATIC CHLORACETAMIDES, THEIR PREPARATION, THEIR USE AS HERBICIDES. - Google Patents

Description

       

    <EMI ID = 1.1>

  
The use of these as herbicides The present invention relates to new 5-membered heteroaromatic compounds relating to a carbon atom

  
  <EMI ID = 2.1>

  
ration, their use as herbicides, agricultural chemicals containing these compounds as active components and facilitating their use, and intermediate products of their preparation.

  
Various nitrogen-substituted α-haloacetanilides are already known which have herbicidal properties.

  
U.S. Patent No. [deg.] 4,282,028

  
  <EMI ID = 3.1>

  
killed with nitrogen having a herbicidal activity and regulating plant growth. There is a need for even more effective herbicides. The 5-membered heteroaromatic compounds according to the invention constitute particularly effective herbicides having the desired persistence in the soil.

  
  <EMI ID = 4.1>

  

  <EMI ID = 5.1>


  
in which

  
Ar represents a 5-membered heteroaromatic group comprising

  
  <EMI ID = 6.1>

  
by a cyclic carbon atom to the nitrogen atom of the N (Y) COCH Cl group to which it is linked, it being specified that, when Ar represents a pyrazolyl group, this N (Y) COCH Cl group is in position 4, and

  
  <EMI ID = 7.1>

  
in which R represents H or a C1-CS alkyl group and

  
  <EMI ID = 8.1>

  
ester or amide function;

  
  <EMI ID = 9.1>

  
  <EMI ID = 10.1>

  
Az is an aromatic heterocycle chosen from the rings

  
di- or triazole linked by one of their atoms

  
  <EMI ID = 11.1>

  
  <EMI ID = 12.1>

  
1 to 3 heteroatoms selected from the group consisting of

  
  <EMI ID = 13.1>

  
this hydrocarbon group being unsubstituted or substituted; or a group

  

  <EMI ID = 14.1>


  
in which R4 represents a chosen hydrocarbon group

  
  <EMI ID = 15.1>

  
substituted or substituted by a halogen chosen from F Cl or Br; or is an allenyl group,

R4 'represents H or has one of the meanings indicated for R4 and

  
A represents a hydrocarbon radical which can be linked

  
to R3 to form a saturated heterocycle containing oxygen, namely 1 or 2 oxygen atoms as a heteroatom, the atoms of N and 0 to which it is linked were separated by a number of carbon atoms up to 'to 3;

  
or represents a group CH-C = NOR

  
R5 R5 '

  
  <EMI ID = 16.1>

  
  <EMI ID = 17.1>

  
R6

  
  <EMI ID = 18.1>

  
The group Ar can be unsubstituted or substituted. When substituted, it can carry substituents in all possible positions; preferred positions for these substituents

  
  <EMI ID = 19.1>

  
chloracetamide, and there may be other substituents. Examples of substituents which are suitable for Ar are the halo-

  
  <EMI ID = 20.1>

  
C3-C6 cycloalkyl groups; formyl or alkanoyl groups

  
  <EMI ID = 21.1>

  
C-C alkynyloxy; hydroxy and hydroxymethyl and their esters (for example their esters of organic carboxylic acids, such as

  
  <EMI ID = 22.1>

  
such as acetic acid or chloracetic acid).

  
Any possible substituent of Ar which is not in the ortho position of the chloracetylamino group substituted for nitrogen is

  
  <EMI ID = 23.1> <EMI ID = 24.1>

  
When Ar contains 2 cyclic heteroatoms, one of them is N and the other is preferably chosen from 0 and S.

  
A preferred subgroup of the compounds of formula I is constituted by the compounds in which Ar contains either a cyclic heteroatom (pyrrolyl, thényl, furannyl), or 2 neighboring cyclic heteroatoms (isoxazolyl, isothiazolyl, pyrazolyl). The

  
nitrogen-substituted chloracetylamino group is preferably attached

  
to the cyclic carbon atom in position &#65533; cyclic heteroatom (s); thus, for example in position 3 when Ar is a pyrrole, thiophene or furan cycle and in position 4 when Ar is a

  
isoxasole, isothazole or pyrazole cycle. A favorite subgroup of

  
this latter group consists of the compounds in which the group Ar is substituted ortho, preferably in ortho-ortho position '

  
of the nitrogen-substituted acetylamino group, especially when the

  
or the substituents are chosen from the group specified above.

  
Any cyclic nitrogen atom may be unsubstituted or substituted; when substituted it is preferably substituted

  
  <EMI ID = 25.1>

  
preferably feels a thiophene, isothiazole or isoxazole cycle,

  
more specifically an isothiazole or thiophene cycle. A particularly preferred subgroup of the compounds of formula ballast consists of the compounds in which Ar represents a thiophene ring, in particular an at least 2,4-disubstituted 3-thienyl ring, especially

  
3-thienyl compounds in which the substituents in posi-

  
  <EMI ID = 26.1>

  
hydrocarbons substituted by a halogen, this halogen is preferably Cl or Br; such a substituted hydrocarbon group is more especially monosubstituted. When Y represents a hydrocarbon group substituted by a halogen, the latter in general is preferably not situated in position 1 when the use is intended as herbicide (these halogenated compounds in position 1 are generally unstable; however, they can be used as intermediates

  
of value for the preparation of other compounds of formula I, for example those in which Y represents an alkoxyalkyl or pyrazolylmethyl group); an appropriate example of such meaning for Y is the 2-Cl-ethyl group.

  
  <EMI ID = 27.1>

  
  <EMI ID = 28.1>

  
contain cycloalkyl or cycloalkenyl groups, these cyclic hydrocarbon groups preferably contain up to 6 carbon atoms.

  
  <EMI ID = 29.1>

  
The expression “ester or amide function” used with reference to the meaning of Y applies to all the functions which can be obtained by reaction of the COOH group of an acid with any organic compound reacting with this acid with elimination of water for example an alcohol, an amine, a mercaptan, an oxime, a hydrazine, a hydrazide or a hydrazone. As examples of suitable esters represented by Y, mention may be made of groups (alkoxy in

  
  <EMI ID = 30.1>

  
represents CH2CH2, this group can be substituted by 1, 2, 3 or 4 -

  
  <EMI ID = 31.1>

  
substituted. When CH2CH2 is disubstituted, the substituents are preferably on different carbon atoms.

  
  <EMI ID = 32.1>

  
When Az represents one of the aromatic heterocycles defined above, the ring can be unsubstituted or substituted; the substituents that are suitable for these meanings of Az <EMI ID = 33.1>

  
  <EMI ID = 34.1>

  
preferably mono- or disubstituted.

  
When Az represents a di- or triazole, it is

  
  <EMI ID = 35.1>

  
1-yl or 1,2,4-triazole-1-yl, unsubstituted or substituted, in particular 1-pyrazolyl, 3,5-di-CH -1-pyrazolyle.

  
When Az represents the 5-membered heterocycle

  
  <EMI ID = 36.1>

  
this cycle is for example a furyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-thia- or oxadiazole or 1,3,4-triazolyl cycle, unsubstituted or substituted, for example by one or two substituents chosen from alkyl groups

  
  <EMI ID = 37.1>

  
  <EMI ID = 38.1>

  
When Az represents a pyrimidine group, this

  
  <EMI ID = 39.1>

  
to R and consists for example of a 2-pyrimidinyl group.

  
When Az is the bicyclic derivative of 2-oxo-1-pyrrolidynyl defined above, the benzo residue may be unsubstituted or substituted, for example by halogens; an example suitable for such significance is the group 2-oxo-1,3-benzothiazole-3-yl and its 4-chlorine derivative.

  
  <EMI ID = 40.1>

  
above, this hydrocarbon group may be unsubstituted or substituted, for example by halogens, cyano groups, a group

  
  <EMI ID = 41.1>

  
  <EMI ID = 42.1>

  
monosubstituted. As examples of such meanings for

  
  <EMI ID = 43.1>

  
pyrazolyle.

  
  <EMI ID = 44.1>

  
A is connected to R to form a cycle, for example are <EMI ID = 45.1>

  
When A is not connected to R3 to form; a ring ,, it is preferably non-aromatic; it is particularly

  
  <EMI ID = 46.1>

  
nitrogen to which it is connected by 1 to 3, preferably 1 or 2 atoms

  
  <EMI ID = 47.1>

  
  <EMI ID = 48.1>

  
A can be unsubstituted or substituted, for example by

  
  <EMI ID = 49.1>

  
mono-substituted.

  
The invention also includes methods of preparing

  
  <EMI ID = 50.1> a) in a first process, one starts from a compound of formula II
  <EMI ID = 51.1>
 in which Ar and Y have the sitnificaticn indicated above, and the OH group of the N-hydroxyacetyl group is replaced by Cl; b) in another process, a compound of formula III is reacted
  <EMI ID = 52.1>
 in which Ar has the meanings indicated above, with a compound of formula IV

  

  <EMI ID = 53.1>


  
in which Y has the meanings indicated above,

  
and L is an eliminable group which can be removed under the conditions of the N-alkylation reaction., c) to prepare a compound corresponding to formula la
  <EMI ID = 54.1>
   <EMI ID = 55.1>

  
  <EMI ID = 56.1>

  
Az 'is a di- or triazole connected by one of its

  
nitrogen atoms at CHR 'and

  
Ar and R3 have the meanings indicated above, we start from a compound of formula V

  

  <EMI ID = 57.1>


  
in which Ar and R 'have the meanings indicated above, which are reacted with a reactive derivative of a compound of formula VI

  

  <EMI ID = 58.1>


  
in which Y has the meanings indicated above, d) another process consists in acylating with nitrogen a compound of formula VII
  <EMI ID = 59.1>
 in which Ar and Y have the meanings indicated above, using chloracetyl chloride or a reactive functional derivative of this chloride.

  
Method a) according to the invention can be implemented by conventional procedures and under known conditions for the substitution of an OH group with a chlorine atom.

  
This substitution can be carried out for example by treating a compound of formula II with a chlorinating agent such as thionyl chloride under conditions known per se for analogous reactions.

  
According to a variant of this chlorination process, the compounds of formula II are first converted into their sulfo- derivatives.

  
  <EMI ID = 60.1>

  
sulfonyl halide and the sulfonyloxylated derivatives are then converted into compounds of formula I sought after by nucleophilic substitution of the sulfonyloxy group with a chlorine atom.

  
The reagents providing the anions Cl necessary for this nucleophilic substitution are, for example, chlorides of

  
  <EMI ID = 61.1> quaternary or 4-dimethylaminopyridine hydrochloride. This substitution is advantageously carried out in CH Ci- or in a two-phase hydro-organic system, in which the organic phase consists, for example, of a hydrocarbon such as toluene, in the presence of an appropriate phase transfer catalyst, preferably hot, for example at a temperature of 40 to 120 [deg.] C.

  
Method b) can be carried out according to conventional procedures, under conditions known for the N-alkylation of amides. The reaction is advantageously carried out in an inert solvent under the reaction conditions, for example dimethoxyethane or acetonitrile or in a two-phase hydroorganic system in the presence of a phase transfer catalyst.

  
The appropriate meanings of L, in formula IV,

  
  <EMI ID = 62.1>

  
  <EMI ID = 63.1>

  
The compounds of formula III are preferably used in the form of a salt, more especially an alkali metal salt, for example a sodium salt. These salts are obtained in the usual way by reacting the compound of formula III with a

  
base such as an amide, a hydride, a hydroxide or an alkali metal alcoholate.

  
To prepare the compounds of formula la by method c), the compounds of formula V are advantageously used in the form of an alkali metal salt, for example sodium. When Y2 is a diou triazole, the compound of formula V can also be used in the form of a compound.N-trialkylsilylated # for example N-trimethylsilyl. The reaction can be carried out in the usual manner.

  
The reaction of process d) can also be carried out in the usual manner, under conditions known for the N-chloroacetylation of amines. When the agent used for this chloraceous-

  
  <EMI ID = 64.1>

  
acid fixing agent, for example K CO.

  
The compounds of formula I can be isolated from the reaction mixture by standard techniques.

  
It will be noted that it is possible, according to conventional procedures, to convert each other from one compound of the invention to another, for example by converting an acid group into an ester group, from a carbonyl group to a oxime, from a haloalkyl group to an ether group (or vice versa), etc.

  
It will also be noted that the compounds of the invention may contain one or more centers of asymmetry and may therefore exist in enantiomeric, diastereoisomeric forms; racemic, or in geometric isomeric forms. In general, in the herbicidal compositions according to the invention, these compounds are used in the mixed state, even if the separation can be carried out by known techniques.

  
  <EMI ID = 65.1>

  
are new and therefore also constitute an object of the invention.

  
The compounds of formula II can be obtained by

  
  <EMI ID = 66.1>

  

  <EMI ID = 67.1>


  
in which Ar has the meanings indicated above, with a carboxylic acid, and subsequent introduction of the

  
  <EMI ID = 68.1>

  
by nitrogen alkylation. These esters are obtained by acylation of the corresponding compounds of formula IX

  

  <EMI ID = 69.1>


  
in which Ar has the meanings indicated above,

  
  <EMI ID = 70.1>

  
The compounds of formula III can also be obtained by acylation of a compound of formula IX using chloracetyl chloride.

  
The compounds of formula V (which in fact constitute a subgroup of the compounds of formula I) can be obtained by reacting a compound of formula IX with an appropriate aldehyde, which gives a Schiff base which is reacted with the chloracetyl chloride.

  
The compounds of formula VII can be obtained by alkylation with nitrogen of a compound of formula IX. This alkylation

  
can be carried out in the usual way, using suitable alkylating agents (for example halides) or, where appropriate, by reduction via the base

  
of Schiff or of the amide.

  
Many of the compounds of formula IX are new.
-A particular group of interesting new compounds of formula IX is constituted by the 3-aminothiophenes substituted in positions 2 and 4 by groups chosen from alkyl groups <EMI ID = 71.1>

  
of formula IXa also constitute an object of the invention.

  
The compounds of formula IX can be obtained by reduction of the corresponding nitro compounds, for example by catalytic hydrogenation under pressure in the presence of palladium.

  
  <EMI ID = 72.1>

  
can be obtained by reduction of the corresponding thiophene-carboxylate using a complex hydride, such as sodium hydride and bis- (methoxyethoxy) aluminum. When appropriate, the compounds of formula IXa can also be obtained from

  
  <EMI ID = 73.1>

  
can be obtained, for example, from the corresponding acids via their azides, followed by a Curtius reaction.

  
When the preparation of a starting product is not described in the present application, the corresponding compound is known or can be prepared and purified by known methods or by methods analogous to those described in the present application or to methods known.

  
The compounds of formula I have a utility because they make it possible to act on plant growth or to modify it. Under the name of plants are designated seeds in the process of germination, shoots emerging from the ground and established vegetation, including underground parts.

  
In particular, the compounds according to the invention can be used as herbicides, as shown inter alia

  
damage to both monocotyledonous and dicotyledonous plants, such as Lepidium sativum. Avena sativa .. Agrostis alba and Lolium perenne in trials at doses corresponding to one

  
  <EMI ID = 74.1>

  
post-emergence. Due to their herbicidal activity, the compounds according to the invention can be used to combat dicotyledonous and grass weeds, as shown by other tests carried out with representative compounds at doses corresponding to an application dose of 0, 2 to 5.0 kg of active ingredient, for example 0.2, 1.0 and 5.0 kg of active ingredient per hectare, on broadleaf weeds, such as Asaranthus retroflexus Capsella bursa.-pastoris, Chenooodium alba, Stellaria Senecio media

  
  <EMI ID = 75.1>

  
  <EMI ID = 76.1>

  
myosuroides, Apera spica-venti, Avena fatua. Echinochloa crus-galli, Bromus tectorum, Sorghum halepense, Digitaria spp and Setaria spp. Other tests indicate a favorable persistence in the soil of the compounds of the invention.

  
The compounds according to the invention are relatively less toxic to crops than to weeds. We observe, among other things, a selective herbicidal activity on corn, soybeans, cotton, sugar beets, potatoes, alfalfa, sunflowers, rapeseed, peanuts or flax, depending among other things on the nature of the compound and application dose. The compounds according to the invention can therefore be used as selective herbicides in places of cultivation.

  
The invention therefore also includes a method for controlling weeds, preferably in places of cultivation, in particular in a place of cultivation as mentioned above, which method consists in applying on the premises an effective herbicidal amount ( a selective herbicidal amount which is effective when the sites are crop borders) of a compound according to the invention. In a particularly preferred embodiment of the invention, a compound of formula I is used in pre-emergence

  
(both cultivated plant and weeds) to selectively combat weeds in growing locations.

  
For the general herbicidal application as for the selective herbicidal application of the compounds according to the invention,

  
the amount to be applied to achieve the desired effect varies according to the nature of the plant cultivated when used in selective application and according to other conventional variables, such as the nature of the compound, the mode of application, the conditions of the treatment and similar factors. The appropriate application doses can be determined by routine techniques well known to specialists, or by comparing the activity of the compounds according to the invention with reference products for which the application dose is known, for example greenhouse tests. In general, however, satisfactory results are usually obtained.

  
by applying the compound at a dose in the range of about

  
  <EMI ID = 77.1>

  
from 0.5 to 3.0 kg / ha, repeating the application when necessary. When the application is made in places of cultivation, the application rate will preferably not exceed 3 kg / ha.

  
  <EMI ID = 78.1>

  
preferably used in the form of herbicidal compositions in combination with one or more diluents acceptable for this use. Suitable formulations contain from 0.01 to 99% by weight of active ingredient, from 0 to 20% of a surfactant acceptable for herbicidal use and from 1 to 99.99% of solid diluents

  
or liquids. Sometimes it pays to work with

  
  <EMI ID = 79.1>

  
active ingredient; this is achieved by incorporating additional surfactant into the formulation or by mixing it in the reservoir.

  
  <EMI ID = 80.1>

  
at 25% by weight of active material. Naturally, the contents

  
in active material may be weaker or stronger depending on the intended application and the physical properties of the compound. The concentrated forms of the products, designed to be diluted before use, generally contain from 2 to 90%, preferably from 10 to
80% by weight of active material.

  
Among the useful formulations containing the compounds

  
according to the invention, there may be mentioned fine powders, granules, granules, concentrated suspensions, wettable powders.

  
emulsifiable concentrates and the like. They are obtained in the usual way, for example by mixing the compounds according to the invention with the diluents. More precisely,

  
the liquid compositions are obtained by mixing the components,

  
fine solid compositions by mixing and usually grinding, suspensions by wet grinding; the granules and granules are obtained by impregnating or coating granular vehicles (previously formed) with the active substance or by

  
agglomeration techniques.

  
The compounds according to the invention can also

  
be used in microencapsulated form.

  
In the herbicide products, additives can also be introduced which make it possible to improve the results obtained with the active material and to reduce the formation, of foam,

  
solidification and; corrosion.

  
The expression "surfactant", as used in the present application, applies to substances which are acceptable for use in herbicidal products and which confer emulsifiable, spreading, wetting properties, dispersibility or other properties modifying the surface state. Examples of surfactants include sodium ligninsulfonate and sodium laurylsulfate.

  
The term diluent, as used in the present application, applies to a liquid or solid material acceptable for use in herbicide products and which serves to dilute a concentrated material to the desired or suitable concentration for use. For fine powders or granules, it may for example be talc, kaolin or diatomaceous earth; for concentrated liquid forms, it may be

  
for example a hydrocarbon, such as xylene, or an alcohol,

  
such as isopropanol, and for liquid application forms, inter alia water or diesel.

  
The compositions according to the invention may also contain other compounds having a biological activity, for example compounds having a similar herbicidal activity

  
or complementary or compounds having an antidote, fungicide or insecticide activity.

  
The examples which follow illustrate the invention without however limiting its scope; in these examples, the indications of parts and percentages are by weight unless otherwise stated.

EXAMPLES

  
Examples of herbicidal compositions will first be described.

  
EXAMPLE A: Wettable powder

  
  <EMI ID = 81.1>

  
example compound n [deg.] 25 below, with 25 parts of fine synthetic silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium ligninesulfonate and 45 parts of fine kaolin and are ground to a medium particle size about 5 microns. We obtain

  
a wettable powder which is diluted with water before being used in the form of a spray liquor at the desired concentration. EXAMPLE B: Emulsifiable concentrate

  
Mix carefully until a solution is obtained

  
  <EMI ID = 82.1>

  
n [deg.] 25 below, 40 parts of xylene, 30 parts of dimethylformamide

  
  <EMI ID = 83.1>

  
  <EMI ID = 84.1>

  
and a polyethoxylated triglyceride from Atlas Chemie GmbH).

  
An emulsifiable concentrate is obtained. diluted in water before use.

  
EXAMPLE C: Granules

  
5 kg of a compound of formula I, for example compound n [deg.] 25 below, are dissolved in 25 l of methylene chloride. The solution is then added to 95 kg of granulated attapulgite (at

  
a particle size of 0.30 to 0.70 mm) and mix carefully. The solvent is then evaporated in vacuo.

  
The examples which follow describe the preparation of the compounds according to the invention; in these examples, the temperatures are indicated in [deg.] C, the pressures in mm Hg and the values of Rf have

  
were obtained on silica gel, unless otherwise indicated.

FINAL COMPOUNDS

  
EXAMPLE 1

  
  <EMI ID = 85.1>

  
  <EMI ID = 86.1>

  
tion, while cooling, 1.31 g (0.0069 mole) of p-toluenesulfonyl chloride in 3.5 ml of toluene. When the heat generated by the reaction has subsided, the stirring is continued for a further 20 hours at room temperature.

  
The toluene layer is separated, washed with water

  
and dried over anhydrous Na2SO4.

  
The crude residue obtained on evaporation of the solvent on a rotary evaporator is recrystallized from ethyl ether;

  
  <EMI ID = 87.1>

  
ylmethyl) -toluene-sulfonyloxyacetamide ("tosylate")
101-103 [deg.].

  
Heated to 90 [deg.] For 6 h and with stirring a mixture of 2.16 g (0.0051 mole) of this tosylate, 1.84 g (0.0066 mole)

  
  <EMI ID = 88.1>

  
The toluene layer is then separated, it is. dried over Na SO, and evaporated in vacuo. The residue is chromatographed on a column of silica gel. Elution with a 2: 1 hexane / ethyl acetate mixture gives the desired compound in the form of crystals of analytical purity melting at 76-78 [deg.].

  
EXAMPLE 2

  
  <EMI ID = 89.1>

  
(process a)

  
To a solution of 2.0 g (0.008 mole) of N- (2,4-

  
  <EMI ID = 90.1>

  
  <EMI ID = 91.1>

  
dry methylene, added with stirring while cooling 0.93 g

  
  <EMI ID = 92.1>

  
dry.

  
  <EMI ID = 93.1>

  
and the methane sulfonate of the starting compound is heated at reflux for 25 h then evaporated in vacuo.

  
The residual oil, after chromatography on a column of silica gel (elution with ethyl ether) solidifies on refrigeration at -20 [deg.]; the product then melts at 54-55 [deg.]. EXAMPLE 3

  
  <EMI ID = 94.1>

  
  <EMI ID = 95.1>

  
  <EMI ID = 96.1>

  
dry dimethoxyethane (= DME), add in portions, with good agitation-

  
  <EMI ID = 97.1>

  
solid chloracetamide.

  
When the addition is complete, the solution is stirred

  
  <EMI ID = 98.1>

  
at room temperature and treated with a solution of 7.25 g

  
  <EMI ID = 99.1>

  
After 4 h of reaction at 50 [deg.], The mixture is filtered.

  
and it is evaporated under vacuum (50 [deg.] / 0.01 mm Hg). The residual brown oil, after chromatography on silica gel (elution with an ethyl ether / hexane mixture, 2: 1) is subjected to distillation in a ball tube; the desired compound is obtained in the analytical purity state

  
  <EMI ID = 100.1>

  
200 ml of methylene chloride and 40 ml of water, 17 g (0.11 mol) of solid 1-chloromethyl-pyrazole hydrochloride are added with good stirring at a speed such that the temperature does not exceed 25 [deg.] .

  
When the addition is complete, the mixture is stirred for a further 2.5 h at room temperature. Another 100 ml of water are added. The organic layer is separated, washed with three 200 ml portions <EMI ID = 101.1>

  
the residue on a column of silica gel. Elution with the hexane / ethyl ether mixture 1: 1, gives the desired compound in the form of syrup of analytical purity which crystallizes by refrigeration overnight at -20 [deg.]; the product then melts at 88-89 [deg.] (after recrystallization from ethyl ether).

  
EXAMPLE 5

  
  <EMI ID = 102.1>

  
9.4 g (0.05 mole) of N- (3,5dimethyl-isoxazole-4-yl) -chloracetamide in 150 ml of acetonitrile are added dropwise

  
  <EMI ID = 103.1>

  
sodium hydride (80% dispersion in mineral oil) in

  
25 ml of dry acetonitrile.

  
When the exothermic reaction (34 [deg.]) Has subsided.

  
the sodium salt solution is allowed to return to room temperature

  
  <EMI ID = 104.1>

  
ethyl propionate in 25 ml of dry acetonitrile.

  
When the addition is complete, the reaction mixture is heated at 50 [deg.] For 3 h, then evaporated to dryness. The residue is taken up in 100 ml of ethyl ether and filtered. The residual oil obtained by evaporation of the filtrate is chromatographed on a column of silica gel. Elution with the ethyl ether / hexane mixture 1: 1, gives the desired compound melting at 49-50 [deg.]. EXAMPLE 6

  
  <EMI ID = 105.1>

  
To a solution of 12.7 g (0.1 mole) of 2,4-dimethyl3-amino-thiophene in 100 ml of dry benzene containing 16 g of sieve

  
0

  
  <EMI ID = 106.1>

  
dropwise with stirring 8.5 ml (0.15 mole) of acetaldehyde, taking care that the temperature does not exceed 25 [deg.].

  
When the addition is complete, the mixture is stirred

  
reaction for another 24 h at room temperature, then filtered. Removal of the solvent gives the Schiff base as a light brown liquid.

  
To the solution of 13 g (0.085 mole) of this substance in 75 ml of dry toluene, added dropwise with stirring

  
  <EMI ID = 107.1>

  
When the addition is complete, the reaction solution is stirred for a further 30 min at -30 [deg.] And then treated dropwise at the same temperature with 12 g (0.085 mole) of 1-trimethylsilyl-pyrazole. When the addition is complete, the acetone / dry ice bath is removed, the mixture is allowed to return to room temperature and stirred for a further 20 h.

  
The reaction mixture is filtered and evaporated in vacuo. The residual syrup is chromatographed on a gel column

  
silica. Elution with the hexane / ethyl ether mixture 3: 2, gives colorless crystals of the desired compound, which melt at
76-78 [deg.] After recrystallization from ethyl ether.

  
EXAMPLE 7

  
  <EMI ID = 108.1>

  
  <EMI ID = 109.1>

  
To a mixture of 6.05 g (0.03 mole) of N- (2-ethoxyethyl) -

  
  <EMI ID = 110.1>

  
  <EMI ID = 111.1>

  
tion, without cooling, the solution of 3.4 g (0.03 mole) of chloroacetyl chloride in 10 ml of CH Cl. When the exothermic reaction (25 [deg.]) Has subsided, the stirring is continued for 4 h at room temperature.

  
The methylene chloride layer is then separated,

  
  <EMI ID = 112.1>

  
under vacuum. The crude desired compound obtained as a residue in fact has analytical purity;

  
Rf = 0.23 (hexane / ethyl ether, 1: 2). A small part of the substance was distilled in the ball tube: the product

  
  <EMI ID = 113.1>

  
  <EMI ID = 114.1>

  
were obtained by one or more of the procedures described in Examples 1 to 7 above (Ne represents CH and Et C H).

T A B L E A U A

  

  <EMI ID = 115.1>
 

  
TABLE A (continued 1)
  <EMI ID = 116.1>
 TABLE A (continued 2)
  <EMI ID = 117.1>
 TABLE A (continued 3)
  <EMI ID = 118.1>
 
  <EMI ID = 119.1>
 Compound

  
n [deg.] Aryle Y Characterization

  
  <EMI ID = 120.1>

  
  <EMI ID = 121.1>

  
85 CH2-OEt F. 24 [deg.]

  
  <EMI ID = 122.1>

  
87 2-Me-4-EtO-thiene-

  
3-yle pyrazolyl-l-CH2

  
  <EMI ID = 123.1>

  
3-yle CH20Et F. 37-38 [deg.]
97a 2-MeCO-4-Et-thiene-

  
  <EMI ID = 124.1>

  
  <EMI ID = 125.1>

  
TABLE A (continued 5)
  <EMI ID = 126.1>
 TABLE A (continued 6)
  <EMI ID = 127.1>
 TABLE A (continued 7)

  

  <EMI ID = 128.1>


  
Intermediate products.

  
EXAMPLE 8

  
  <EMI ID = 129.1>

  
A solution of 45.2 g (0.21 mole) of methyl 3,5-dimethyl-4-nitro-thiophene-2-carboxylate is hydrogenated in 1000 ml of methanol for 2 h, under a pressure of 10 bars, presence

  
4.5 g of palladium (10% on charcoal).

  
When the reduction is complete, the mixture is filtered, the catalyst is washed with methanol and the filtrate is evaporated to dryness.

  
The crystallized residue is treated with ethyl ether; the desired compound is obtained in the analytical purity state, melting at 88-89 [deg.].

  
EXAMPLE 9

  
  <EMI ID = 130.1>

  
A solution of 100 g (890 ml (3 moles) of sodium hydride and bis- (2-methoxyethoxy) aluminum (70% solution in toluene) and 600 ml of dry toluene is added dropwise with vigorous stirring. 0.58 mol) of methyl 3-amino-4-methyl-thiophene-2-carboxylate in 700 ml of dry toluene at a speed such that the temperature does not exceed 55 [deg.].

  
When the addition is complete, stirring is continued for a further 30 min, then the reaction mixture is carefully added in small portions, at 0 [deg.], To 1200 ml of a solution

  
  <EMI ID = 131.1>

  
  <EMI ID = 132.1>

  
and evaporated under vacuum. The residual brown liquid is distilled under vacuum; the desired compound is obtained in the analytical purity state boiling at 49-52 [deg.] / 0.01 mm Hg.

  
EXAMPLE 10

  
  <EMI ID = 133.1>

  
The mixture is refluxed for 2 h with good stirring a mixture of 55.4 g (0.2 mole) of benzyl N- (4-methoxy-2-methyl-thiene-3yl) carbamate, 40 g (0.7 mole ) of KOH, 600 ml of ethanol and 120 ml of water. The solution is evaporated in vacuo and the residue is diluted with 500 ml of water. The light yellow oil which separates is taken up in 400 ml of ethyl ether and the aqueous phase is extracted once with 400 ml of ether.

  
  <EMI ID = 134.1>

  
and we filter. We pass through the filtrate for 30 min a slow

  
  <EMI ID = 135.1>

  
  <EMI ID = 136.1>

  
The hydrochloride of the desired compound which precipitates melts at 230 [deg.] (The free base melts at 61-63 [deg.]).

  
EXAMPLE 11

  
  <EMI ID = 137.1>

  
6 g (0.22 gram atom) of aluminum amalgam are added

  
  <EMI ID = 138.1>

  
thio-4-methyl-3-nitrothiophene in solution in 200 ml of wet ethyl ether. The vigorous reaction which starts within 5 to 10 minutes is kept under control by cooling the flask in ice.

  
After 45 min, when the exothermic reaction has subsided and all the aluminum has reacted, we add another

  
6 g of amalgamated aluminum.

  
The reaction mixture is then brought to moderate reflux for 2 h; during this period, the formation of thiophene-amine is complete. The organic phase is decanted and the remainder is washed with two 50 ml portions of ethyl ether. We dry them

  
  <EMI ID = 139.1>

  
The desired compound obtained as a residue in the raw state is distilled

  
  <EMI ID = 140.1>

  
EXAMPLE 12

  
Compounds of formula IX which have been obtained according to one or more of the procedures described in Examples 8 to 11 have been listed below.

  
  <EMI ID = 141.1>

  
Example 12.3 4-C2H5-2-CH2-3-aminothiophene (Rf = 0.25, ethyl ether / hexane, 2: 1)

  
  <EMI ID = 142.1>

  
  <EMI ID = 143.1>

  
  <EMI ID = 144.1>

  
  <EMI ID = 145.1>

  
methylene, 15 g are added dropwise at room temperature
(0.11 mole) of acetoxyacetyl chloride.

  
When the exothermic reaction has subsided, stirring is continued for another 1 h. We evaporate the organic layer

  
  <EMI ID = 146.1>

  
The solid residue is treated with hexane; the desired compound is obtained in the analytical purity state melting at 110-112 [deg.].

  
EXAMPLE 14

  
  <EMI ID = 147.1>

  
A moderate stream of ammonia gas is passed for 30 min with stirring in a solution of 15.9 g (0.07 mole)

  
  <EMI ID = 148.1>

  
methanol.

  
When the exothermic reaction (40 [deg.]) (Moderate by intermittent cooling in cold water) has subsided, the stirring is continued for a further 30 min, then the solution is evaporated to dryness. The solid obtained is recrystallized from ethyl acetate; the desired compound is obtained in the analytical purity state in the form of colorless crystals melting at 85-87 [deg.]. EXAMPLE 15

  
  <EMI ID = 149.1>

  
At 70 ml (0.245 mole) of sodium hydride and bis-
(2-methoxyethoxy) aluminum (70% solution in toluene) and 30 ml of dry toluene, a solution is added dropwise with stirring

  
  <EMI ID = 150.1>

  
acetamide in 125 ml of dry toluene. When the exothermic reaction has subsided, the stirring is continued for another 90 min, then

  
add the reaction solution carefully, in small

  
  <EMI ID = 151.1>

  
The toluene layer is separated and the aq &#65533; wear phase is extracted twice with 100 ml of toluene. The combined toluene solutions are dried over Na2SO4 and evaporated in vacuo. The light brown liquid obtained as a residue is of analytical purity; Rf = 0.32 (hexane / ethyl ether, 1: 2).

  
EXAMPLE 16

  
  <EMI ID = 152.1>

  
The 6.4 g solution is boiled under reflux
(0.05 mole) of 2,4-dimethyl-3-amino-thiophene and 5.3 g (0.06 mole) of methoxyacetone in 100 ml of dry toluene until separation of the theoretical amount of water in the trap (2.5 h). The toluene solution is allowed to cool to room temperature and evaporated in vacuo. The residual gross Schiff base is sufficiently

  
pure for the next operation.

  
9.2 (0.048 mole) of this substance is dissolved in
100 ml of dry toluene and added without cooling, with good stirring, to a solution of 28 ml (0.098 mole) of sodium hydride

  
  <EMI ID = 153.1>

  
toluene) in 15 ml of dry toluene.

  
When the exothermic reaction (44 [deg.]) Has subsided, the mixture is stirred for another 90 min, then the brown reaction solution is carefully added, in small portions, at -10 [deg.], To 40 ml of 20% KOH solution.

  
The toluene layer is then separated, dried over Na2SO4 and evaporated in vacuo. The residual oil, after chromatography on a silica gel column (elution with a hexane / ethyl ether mixture, 3: 1) is distilled under vacuum (using a

  
  <EMI ID = 154.1>

  
EXAMPLE 17

  
  <EMI ID = 155.1>

  
amine.

  
Stirred for 20 h at 80 [deg.] A mixture of 12.7 g
(0.1 mole) 2,4-dimethyl-3-amino-thicphene, 14.6 g (0.1 mole)

  
  <EMI ID = 156.1>

  
of K2CO3 in 150 ml of dry dimethylformamide (DMF).

  
It is then cooled to room temperature, the reaction mixture is poured into 400 ml of water and the aqueous DMF solution is extracted with three 150 ml portions of ethyl ether. The combined ether extracts are dried over anhydrous Na2SO4 and evaporated in vacuo. The residual brown oil is chromatographed on a column of silica gel; elution with a hexane / ethyl ether mixture 1: 1, gives the desired compound in the form of an orange liquid of analytical purity, Rf = 0.2 (ether / hexane, 1: 1).

  
EXAMPLE 18

  
  <EMI ID = 157.1>

  
Stir for 24 h at room temperature 82 g
(0.412 mole) of methyl ether of N- (2,4-dimethyl-thiene-3yl) glycine and 42 g (1.3 mole) of hydrazine hydrate in 350 ml of alcohol. The mixture is evaporated in vacuo. After adding 150 ml of water, the residue is treated with 4 portions of 500 ml of ether. The ether phase is dried over Na2SO4 and evaporated to dryness; the desired compound of analytical purity is obtained, melting at 68-70 [deg.]. EXAMPLE 19

  
  <EMI ID = 158.1>

  
A mixture of 15 g is brought to reflux for 4 h.
(0.075 mol) of N- (2,4-dimethyl-thiene-3-yl) glycine hydrazide and 5.5 g (0.075 mol) of methylisothiocyanate in 100 ml of ethanol. The reaction mixture is cooled to 10 [deg.] C and the precipitate formed is separated by filtration; the pure compound is obtained which melts at
184-187 [deg.].

  
EXAMPLE 20

  
  <EMI ID = 159.1>

  
the reaction mixture at room temperature for 5 h, the organic layer is separated, washed with three 100 ml portions of water,

  
dried over Na2SO4 and evaporated to dryness. We recrystallize the residue

  
twice in ether; the desired compound is obtained in the pure state, melting at 92-96 [deg.].

  
EXAMPLE 21

  
  <EMI ID = 160.1>

  
5.5 g (0.05 mole) are added dropwise to 10 g (0.05 mole) of N- (2,4-dimethylthiene-3-yl) -glycine hydrazide in 175 ml of methylene chloride ) acetic anhydride. We shake

  
the mixture for 1 h at 20 [deg.] C and evaporated to dryness. The oily residue is redissolved in 150 ml of pyridine and 1 g (0.05 mole) of phosphorus pentasulfide is added in small portions. During the course of the addition, the temperature reaches 48 [deg.] C. The mixture is brought to reflux for 2 h and stirred at room temperature for a further 16 h. After evaporation to dryness, the residue is redissolved in

  
methylene chloride and the solution is treated successively with ice water, a dilute solution of cold sodium hydroxide and water, dried over Na2SO4 and evaporated to dryness. Chromatography on a column of silica gel gives the pure compound in the oil state, Rf = 0.23 (ethyl acetate / hexane, 6: 4). EXAMPLE 22

  
  <EMI ID = 161.1>

  
methvl) amine

  
To a solution of 2.2 g (0.055 mole) of NaOH in
125 ml of methanol, 5 g (0.05 mole) of acetamidine hydrochloride are added with stirring. 15 min later, add 10 g
(0.05 mol) of N- (2,4-dimethyl-thiene-3-yl) -glycine hydrazide and the mixture is brought to reflux for 18 h. After evaporation to dryness, the residue is treated with methylene chloride and the insoluble side products are filtered. Evaporation of the methylene chloride gives the desired compound melting at 85-87 [deg.]. EXAMPLE 23

  
  <EMI ID = 162.1>

  
in 50 ml of acetone. The desired compound is obtained which crystallizes in the pure state, by filtration; it melts at 126-128 [deg.].

  
EXAMPLE 24

  
The compounds of formula VII identified below were obtained by one or more of the procedures for

  
example 13 to 23 above:

  

  <EMI ID = 163.1>
 

  

  <EMI ID = 164.1>
 

  
EXAMPLE 25

  
  <EMI ID = 165.1>

  
At 12.25 g (0.066 mole) of 3,5-dimethyl-4-amino-

  
  <EMI ID = 166.1>

  
25 ml of water and 150 ml of methylene chloride, added without

  
  <EMI ID = 167.1>

  
When the exothermic reaction (36 [deg.]) Has subsided, the mixture is stirred for another 1 h. The organic layer is then separated, washed with water and dried over NaSO. anhydrous. Removal of the solvent gives the desired product in the form of colorless crystals melting at 157-158 [deg.].

  
EXAMPLE 26

  
  <EMI ID = 168.1>

  
  <EMI ID = 169.1>

  
sulfuryl chloride.

  
After the addition is complete, the reaction mixture is allowed to return to room temperature and stirred for a further 20 h. The solvent is then removed in vacuo and the crystallized residue is triturated with hexane; the desired compound is obtained in the analytical purity state melting at 166 [deg.] (decompositi.on).

  
EXAMPLE 27

  
  <EMI ID = 170.1>

  
and 7 drops of concentrated HC1.

  
After standing for 30 h at room temperature, the reaction mixture is evaporated in vacuo (50 [deg.] / 0.01 mm Hg) and the residual brown syrup is chromatographed on a column of silica gel. Elution with a 2: 1 hexane / ethyl ether mixture gives the desired compound in the form of colorless crystals melting at 57-58 [deg.].

  
EXAMPLE 28

  
  <EMI ID = 171.1>

  
A solution of 1.5 g (0.0065 mole) of N- (2-acetyl-4-methyl-thiene-3-yl) -chloracetamide and 6.6 g (0.14 mole) is brought to reflux for 7 h. ) methoxyamine in 50 ml of

  
o

  
dry toluene containing 5 g of 3A molecular sieve.

  
The yellow reaction solution is then filtered and evaporated to dryness. The crude mixture of syn / anti isomers obtained is separated by chromatography with a hexane / ethyl ether mixture as mobile phase.

  
  <EMI ID = 172.1>

  
syn) melting at 101-102 [deg.] (Rf = O, 33, hexane / ether, 1: 1). Continued elution of the silica gel column gives the other anti-isomer, analytical purity (0.4 g) melting at 87-89 [deg.] (Rf = 0.21). EXAMPLE 29

  
The compounds of formula III identified below were obtained by one or more of the procedures of Examples 25 to 28
  <EMI ID = 173.1>
 EXAMPLE 30

  
  <EMI ID = 174.1>

  
dry (DMF) with good stirring, to a suspension of 3.0 g (0.1 mole)

  
  <EMI ID = 175.1>

  
  <EMI ID = 176.1>

  
When the exothermic reaction (50 [deg.]) Has subsided, the solution of the sodium salt is allowed to return to ambient temperature, then it is treated with a solution of 10.4 g (0.11 mole) of oxide

  
  <EMI ID = 177.1>

  
addition, the mixture is heated to 100 [deg.] for 4 h and then evaporated

  
  <EMI ID = 178.1>

  
The residue is taken up in 200 ml of ethyl ether. washed with 250 ml of water, dried (MgSO.) and filtered. The residual oil obtained on evaporation of the filtrate is chromatographed on a column of silica gel. Elution with ether gives the desired product in the form of a viscous liquid of analytical purity

  
  <EMI ID = 179.1>

  
EXAMPLE 31

  
The compounds of formula II below for which Ar is the 2,4-dimethylthiene-3-yl group were obtained by the procedure of Example 30.

  

  <EMI ID = 180.1>
 

  
EXAMPLE 32

  
  <EMI ID = 181.1>

  
To 9.8 g (0.068 mole) of 4-methoxy-2-methyl-3-aminothiophene, 9.45 g (0.068 mole) of K2CO3, 35 ml of water and 100 ml of CH Cl are added without cooling a solution 8.4 g (0.069 mole) of ethoxyacetyl chloride in 20 ml of CH Cl.

  
When the exothermic reaction (32 [deg.]) Has subsided,

  
stir for another 1 h. The organic layer is then separated, washed twice with 150 ml of water and dried over NaSO. anhydrous.

  
The residue obtained on evaporation of the solvent on a rotary evaporator is subjected to chromatography on a column of silica gel. Elution with a hexane / ethyl ether mixture, 1: 1, gives the desired compound in the analytical purity state melting at 40-41 [deg.]. EXAMPLE 33

  
The amides of formula ArNHCOY., Below were obtained by a procedure analogous to that of Example 34.

  

  <EMI ID = 182.1>


  
EXAMPLE 34

  
  <EMI ID = 183.1>

  
63.6 g are added all at once, with stirring
(0.23 mole) diphenylphosphorylazide and 24.4 g (0.23 mole) tri-

  
  <EMI ID = 184.1>

  
2-methyl-thiophene-3carboxylic acid in 300 ml of dry benzene.

  
The mixture is brought to reflux for 1 h, then treated with 25 g (0.23 mole) of benzyl alcohol.

  
  <EMI ID = 185.1>

  
rature room, diluted with 350 ml of ethyl ether and washed successively with 250 ml of 5% HCl, 250 ml of saturated solution

  
of NaHCO.- and 200 ml of saturated brine. The crystallized residue obtained

  
  <EMI ID = 186.1>

  
is triturated with pentane; we obtain the desired compound of

  
  <EMI ID = 187.1>

  
EXAMPLE 35

  
Following the procedure of Example 34, with the appropriate carboxylic acid, the following carcamates were obtained.

  
  <EMI ID = 188.1>

  
melting at 83 [deg.].

  
EXAMPLE 36

  
  <EMI ID = 189.1>

  
This compound was obtained by saponification (KOH) of the corresponding ethyl ether; it melts at 127 [deg.]. EXAMPLE 37

  
By a procedure analogous to that of Example 36,

  
  <EMI ID = 190.1>

  
melting at 66-68 [deg.].

  
EXAMPLE 38

  
  <EMI ID = 191.1>

  
20 ml of 50% sodium hydroxide solution are added dropwise to a mixture of 18.6 g (0.1 mole) of 4-hy droxy-2-

  
  <EMI ID = 192.1>

  
dimethyl fate and 2.3 g (0.01 mole) of benzyltriethylammonium chloride in 100 ml of CH Cl at room temperature.

  
After approximately 15 min of boiling at reflux, the desired compound is isolated from the reaction mixture; Rf = 0.36 (ethyl ether / hexane, 2: 1).

  
EXAMPLE 39

  
  <EMI ID = 193.1>

  
Methyl 3,5-dimethylthiophene-2-carboxylate in 200 ml of glacial acetic acid, a mixture of 30 ml of fuming nitric acid (density = 1.5) and 120 is added dropwise over 40 min with good stirring ml of acetic anhydride. After the end of the addition, the brown solution is added again for 2 h at 5 [deg.] Then

  
it is poured into 3 1 of ice water.

  
The aqueous phase is extracted twice with 500 ml of ethyl ether. The ethereal extracts are washed with water and then with

  
  <EMI ID = 194.1>

  
it is evaporated under vacuum.

  
The residue is subjected to chromatography on a column of silica gel. Elution with hexane / ethyl ether
10: 1 gives the desired compound melting at 87-88 [deg.].

  
'' EXAMPLE 40

  
  <EMI ID = 195.1>

  
  <EMI ID = 196.1>

  
dimethyl-5-ethoxy-4-nitropyrazole; Rf = 0.37 with ethyl ether / silica gel.

  
Herbicide activity testing

  
EXAMPLE 41

  
  <EMI ID = 197.1>

  
Seedling pots (7 cm in diameter) are filled with a mixture of peat and sand-based growing medium. On the exposed surface of the mixture of culture substrate and sand, a liquid containing a compound according to the invention is sprayed (for example formulated as described in Example B) and sown in

  
  <EMI ID = 198.1>

  
sativa and Lolium perenne; the seeds of Avena sativa and Lolium perenne, after sowing, are covered with a thin layer
(0.5 cm) of the growing medium / sand mixture. The pots are kept for 21 days at room temperature during lighting
(daylight or equivalent) from 2 to 5 p.m. per day.

  
The herbicidal effect of the particular active compound is determined after the 21 day period. This determination includes a visual assessment of the degree and quality of the damage inflicted on the various plants sown.

  
The compounds of formula I are applied as described above at doses corresponding to 1.4 and 5.6 kg of active material per hectare.

  
A herbicidal activity is observed, that is to say significant damage to the plants subjected to the tests.

  
EXAMPLE 42

  
  <EMI ID = 199.1>

  
A procedure analogous to that of Example 41 is followed except that the compounds subjected to the tests (herbicides) are applied while the plants are in the 2 to 4 leaf stage, the seedlings of the seeds having been staggered so that the plants reach the 2-4 leaf stage at about the same time.

  
Here again, the compounds of formula I are applied as described above at doses corresponding to 1.4 kg / ha and

  
  <EMI ID = 200.1>

  
after the application of the compounds and consists of an assessment analogous to that described in Example 41. A herbicidal activity is observed.

  
EXAMPLE 43

  
Compounds representative of the invention are subjected to tests by the procedure described below (pre-emergence application).

  
Seed trays measuring 30 x 40 cm at a depth of 6 cm are filled with a mixture of peat and sand-based growing medium. An aqueous liquid (formulated for example as described in Example B) containing a compound according to the invention at a determined concentration is applied to the exposed surface of the mixture of culture substrate and sand. The spray volume corresponds to 600 l of liquid

  
aqueous per hectare. The same test is repeated with various concentrations of the liquid, these concentrations being chosen so as to correspond to the desired application doses. In each

  
tray, we then sow six species of seeds. The number of seeds sown for each plant species depends on the germination potential of the seeds and also on the initial growth dimension of the particular plant sown. After sowing, the treated surface is covered with a thin layer about 0.5 cm thick in the mixture of peat and sand-based growing medium.

  
The seed trays are then maintained for

  
28 days at a temperature of 20 to 24 [deg.] C with lighting for

  
2 to 5 p.m. per day.

  
The herbicidal effect of the particular compound of the invention is determined after the 28 day period. This determination consists of a visual assessment of the degree and quality of the damage inflicted on the various plants. Particularly advantageous herbicidal properties are observed, inter alia, with compounds n [deg.] 25, 26, 47, 48, 55, 75, 84

  
and 86 of Table A. Some of the results obtained at an application dose corresponding to 1 kg of active material per hectare are reported in Table B below.

  
EXAMPLE 44

  
  <EMI ID = 201.1>

  
Representative compounds of formula I are subjected to other tests according to a post-emergence application procedure analogous to the pre-emergence test described in example 43, the only difference being that the herbicidal liquid is applied. when the plants have reached stage 2 to

  
4 sheets. To this end, the various plant species are sown at times staggered in time. The conditions prevailing in the greenhouse (temperature, light) are the same as in Example 43. The determination of the herbicidal effect is also made 28 days after application by the procedure of Example 41.

  
Particularly advantageous herbicidal properties are observed, inter alia, with compounds n [deg.] 25, 26, 47, 48, 55, 75,
84 and 86 of Table A. Some of the results obtained at application doses corresponding to 5 kg of active material per hectare are reported in Table C below.

  

  <EMI ID = 202.1>
 

  

  <EMI ID = 203.1>


  
  <EMI ID = 204.1> Full field test

  
Compound n [deg.] 25 was also subjected to a real test, in pre-emergence application, on multiple cultures
(Multicrop-Fieldscreening) under the following conditions:
- Soybean crops ("Steele") (So)

  
Cotton ("Stoneville 213") (Cot)

  
But (LG 11) (Co)

  
  <EMI ID = 205.1>
- Bad Alopecurus pratensis (Al) Echinochloa crus galli (Ech) herbs

  

  <EMI ID = 206.1>


  
(All weeds, except Alopecurus pratensis which has been sown, grow naturally).

  
- Sprayed volume: 750 1 / ha
- Number of repeated applications: 3
- Assessment: 28 days after application <EMI ID = 207.1> 2-methoxyethyl) acetanilide].

  
The following herbicidal activity was observed:

  

  <EMI ID = 208.1>


  
The results reported in the table above indicate a herbicidal activity equal to or greater than that of the commercial products used as comparative controls on monocotyledonous weeds, and greater than that of these comparative products on dicotyledonous weeds. The herbicidal activity is selective for soybeans, cotton and, at the lowest application rate, also for corn.


    

Claims (1)

CLAIMS S 1 - Heteroatomatic chloracetamides corresponding to formula I  <EMI ID = 209.1> in which Ar is a 5-membered heteroaromatic group comprising 1 or 2 cyclic heteroatoms chosen from 0, S and N, and linked by a cyclic carbon atom <EMI ID = 210.1> connected-, it being specified that, when Ar represents a  <EMI ID = 211.1> tion 4, and Y represents an allenyl group, CH -CH = C = CH or represents a hydrocarbon group chosen from  <EMI ID = 212.1> hydrocarbon group being unsubstituted or substituted by a halogen chosen from F. Cl and Br;  <EMI ID = 213.1> in which R represents H or an alkyl group '&#65533; 5 &#65533;  <EMI ID = 214.1> connected, an ester or amide function;  <EMI ID = 215.1> in which R represents CH2 or CH2-CH2 which is unsubstituted or substituted by a C1-C5 alkyl group and Az is a chosen aromatic heterocycle among the di- or triazole heterocyclics linked by one of their atoms  <EMI ID = 216.1> 5 links linked by a car atom  <EMI ID = 217.1> 1 to 3 heteroatoms chosen from 0, <EMI ID = 218.1> R is a 2-oxo-1-pyrrolidinyl group  <EMI ID = 219.1>  <EMI ID = 220.1> 5-oxo and / or bicyclic benzocondenses of such a 2-oxo-lpyrrolidinyl group,  <EMI ID = 221.1>  <EMI ID = 222.1> selected from the alkyl groups in  <EMI ID = 223.1>  <EMI ID = 224.1>  <EMI ID = 225.1> hydrocarbon being unsubstituted or substituted; or a group  <EMI ID = 226.1> in which R represents a group hydrocarbon selected from alkyl groups in  <EMI ID = 227.1>  <EMI ID = 228.1>  <EMI ID = 229.1>  <EMI ID = 230.1>  <EMI ID = 231.1>  <EMI ID = 232.1> carbonaceous being unsubstituted or substituted by halogens chosen from F, Clou Br; or represents an allenyl group #; R4 'represents Hou has one specific meanings  <EMI ID = 233.1> and A is a hydrocarbon radical which can be connected to R3 to form a saturated hetero-cycle containing oxygen in the proportion of 1 or 2 oxygen atoms as a heteroatom, the atoms of N and 0 to which it is connected being separated by a number of carbon atoms of up to 3;  <EMI ID = 234.1>  <EMI ID = 235.1>  <EMI ID = 236.1> above,  <EMI ID = 237.1>  <EMI ID = 238.1>  <EMI ID = 239.1>  <EMI ID = 240.1> R6  <EMI ID = 241.1> CI-C3.  <EMI ID = 242.1> in that Ar is at least substituted in the ortho position of the chloroacetamide group by a substituent chosen from halogens, C1-C4 alkyl groups which are unsubstituted or substituted by halo-  <EMI ID = 243.1>  <EMI ID = 244.1> C1-C4 alkoxy groups; C3-C6 cycloalkyl groups; the  <EMI ID = 245.1> unsubstituted or substituted by halogens or alkoxy  <EMI ID = 246.1> their esters.  <EMI ID = 247.1> in that Ar contains either a cyclic heteroatom or two neighboring cyclic heteroatoms, the heteroaromatic ring being at least disubstituted in position o, o 'of the chloroacetamide group by  <EMI ID = 248.1> optional additional substituent of this heteroaromatic nucleus <EMI ID = 249.1>  <EMI ID = 250.1>  <EMI ID = 251.1> in that Ar represents a substituted thiophene, isothiazole or isoxazole ring.  <EMI ID = 252.1> this Ar represents a substituted thiophene or isothazole ring. 6 - Compounds according to claim 5, characterized in that Ar represents a substituted thiophene ring.  <EMI ID = 253.1> what Ar represents a 3-thienyl group disubstituted in position  <EMI ID = 254.1>  <EMI ID = 255.1> 8 - Compounds according to any one of claims  <EMI ID = 256.1>  <EMI ID = 257.1> claim 1.  <EMI ID = 258.1>  <EMI ID = 259.1> a monomethyl derivative of these groups and R represents an alkyl group  <EMI ID = 260.1> 10 - Compound of formula I according to claim 9, chosen from the group formed by the compounds for which Ar and Y respectively represent <EMI ID = 261.1> ethyl, <EMI ID = 262.1> <EMI ID = 263.1> g) a 2-methyl-4-methoxy-thiene-3-yl group and a pyrazolyl- group 1-methyl,  <EMI ID = 264.1> <EMI ID = 265.1>  <EMI ID = 266.1> formula II  <EMI ID = 267.1> in which Ar and Y have the meanings indicated above, the OH group of the N-hydroxyacetyl group is replaced by a chlorine atom. 12 - Process for the preparation of the compounds of formula I  <EMI ID = 268.1> a compound of formula III  <EMI ID = 269.1> in which Ar has the meaning indicated above, with a compound of formula IV  <EMI ID = 270.1> in which Y has the meanings indicated above and L represents a removable group which can be removed under the conditions of the N-alkylation reaction.  <EMI ID = 271.1>  <EMI ID = 272.1>  <EMI ID = 273.1>  <EMI ID = 274.1>  <EMI ID = 275.1>  <EMI ID = 276.1> nitrogen atoms and Ar and R3 have the meanings given in claim 1, characterized in that a compound of formula V is reacted  <EMI ID = 277.1>  v in which Ar and R 'have the meanings indicated above, with a reactive derivative of a compound of formula VI  <EMI ID = 278.1> in which Y2 has the meanings indicated above.  <EMI ID = 279.1> according to claim 1, characterized in that one acylates with nitrogen  <EMI ID = 280.1>  <EMI ID = 281.1> in which Ar and Y have the meanings indicated above, by chloracetyl chloride or a reactive functional derivative of this chloride. 15 - Use of a compound according to any one of claims 1 to 10 as a herbicide. 16 - Use according to claim 15, characterized in that the compound is used as a selective herbicide. 17 - Use according to claim 16, in crops of sugar beets, cotton, potatoes, scj a, corn or peanuts. 18 - Herbicidal composition, characterized in that it  <EMI ID = 282.1> any one of claims 1 to 10, in association with an agriculturally acceptable diluent. 19 - New compounds chosen from the compounds. of formula II  <EMI ID = 283.1> in which Ar and Y have the meanings indicated in the res  <EMI ID = 284.1> the compounds of formula III  <EMI ID = 285.1>  <EMI ID = 286.1> the compounds of formula VII  <EMI ID = 287.1> in which Ar and Y have the meanings indicated in the res  <EMI ID = 288.1> 3-aminothiophenes substituted in positions 2 and 4 by groups  <EMI ID = 289.1> 20.- Products and processes in substance as above described with reference to the examples cited.