FR2530631A1 - SUBSTITUTED 3-AMINOTHIOPHENES - Google Patents

Abstract

THE INVENTION CONCERNS 3-AMINOTHIOPHENS SUBSTITUTED IN POSITION 2 AND 4 BY ALKYL GROUPS IN C-C AND OR ALCOXY IN C-C. THESE COMPOUNDS CAN BE USED FOR THE PREPARATION OF HERBICIDE PRODUCTS.

Description

The present invention relates to novel

  5-membered heteroaromatic carbon atoms

  a nitrogen-substituted chloroacetylamino group, their prepara-

  their use as herbicides, to Chinese products,

  for agriculture containing these compounds as a

  active and facilitating their use, and to intermediate products

of their preparation.

f

  Various substituted α-haloacetanilides are already known.

  killed with nitrogen having herbicidal properties.

  U.S. Patent No. 4,282,028

  discloses substituted (N-2,5-dialkyl-pyrrole-1-yl) haloacetamides

  Nitrogen killed with herbicidal and regulating activity of plant growth There is a need for even more effective herbicides The 5-membered heteroaromatic compounds of this invention are particularly effective herbicides

  possessing the desired persistence in the soil.

  The compounds according to the invention correspond to formula I

COCH C 1

  Ar NI wherein Ar represents a 5-membered heteroaromatic group comprising 1 or 2 ring heteroatoms selected from O, S and N and connected by a cyclic carbon atom to the nitrogen atom of the group N (Y) COII 2 C 1 to which it is attached, it being specified that when Ar represents a pyrazolyl group, this N (Y) CO Clt 2 Cl group is in the 4-position, and Y is the allenyl group, CH 2 -CH = C = CH 2, or hydrocarbon group selected from C1-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C8cycloalkyl, C8-C8cycloalkenyl, (C3-3cycloalkyl) C>) - C 1 -C 5 alkyl, this hydrocarbon group being unsubstituted or substituted by a halogen selected from FC 1 or Br; or represents a CH (R) -COY group, wherein R 1 represents H or a C 1 -C 5 alkyl group and Y 1 forms, with the -CO group to which it is attached, an ester or amide function ; or represents a group R 2 -A, wherein R 2 represents CH or CH 2 -CH 2 which is unsubstituted or substituted

2 2 2

  with a C 1 -C 5 alkyl group and Az is an aromatic heterocyclic ring selected from di or triazole rings connected by one of their nitrogen atoms to R 2 a 5-membered heterocycle connected by a carbon atom of the same ring at R 2 and containing 1 to 3 heteroatoms selected from the group consisting of O, S and ND and a pyrimidine group, orbyl Az is a 2-oxo-1-pyrrolidinyl group in which a group

  CH 2 can be replaced by 0, S or NCH 3 and the derivatives

  5-oxo and / or bicyclic benzo-neat derivatives of such a 2-ozo-1-pyrrolidinyl group, or is a group A-O-R 3, wherein R 3 is H, a hydrocarbon group selected from C-alkyl groups. 1-C 8, C 3 -C 8 C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 8 -C 8 cycloalkenyl or (C 3 -C 8 cycloalkyl) C 1 -C 8 alkyl

  this hydrocarbon group being unsubstituted or substituted

kill; or a group

-R 4 '

  Wherein R 4 is a hydrocarbon group selected from C 1 -C 5 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl, C 3 -C 8 cycloalkyl, C -C cycloalkenyl 8, (C 3 -C 8 cycloalkyl) C 1 -C 5 alkyl, this hydrocarbon group being unsubstituted or substituted by a halogen selected from FC 1 or Br; or is an allenyl group,

  R 4 represents H or has one of the significances

  R 4 and A represent a hydrocarbon radical which can be connected to R 3 to form a saturated oxygen-containing heterocycle, ie 1 or 2 oxygen atoms as a heteroatom, N atoms. and O to which it is attached and are separated by a number of carbon atoms up to 3; or represents a group CH = NOR 4 I RR 'in which R has the meanings indicated above, R and R are each, independently, H or CH 3, or R 5 forms with R' a group (CH 2) 3 or (CH 2) 4 or represents a CH-N (CH 3) COCH 3 R 6 group

  in which R 6 represents H or a C 1 -C 3 alkyl group.

  The Ar group may be unsubstituted or substituted.

  When substituted, it can carry substituents in all possible positions; the preferred positions for these substituents are the ortho positions, in particular the O 'O positions of the chloroacetamide group, and there may be other substituents such as

  Examples of suitable substituents for Ar are the halo

  genes selected from F, C 1 and Br; unsubstituted or substituted C 1 -C 4 alkyl groups (F, Cl, Br), C 1 -C 4 alkoxy, or C 3 -C 6 cycloalkyl; C 2 -C 4 alkenyl groups unsubstituted or substituted by C 1 -C 4 alkoxy groups; C 3 -C 6 cycloalkyl groups; formyl or C 2 -C 4 alkanoyl groups and their functional derivatives such as their oximes and acetals (for example C (= NO C 1 -C 4 alkyl) -C 1 -C 3 alkyl, C (O-alkylen) C 1 -C 4) 2-C 1 -C 3 alkyl, CH (O-C 1 -C 4 alkyl) 2 etc.); C 1 -C 4 -alkyl, (C 1 -C 5) -alkyl, (C 1 -C 5) -alkyl-C 2 -C 5 -alkoxycarbonyl, unsubstituted C 1 -C 4 -alkoxy or substituted by halogen, C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, hydroxy and hydroxymethyl and their esters (for example, organic carboxylic acid esters, such as formic acid, a C 2 -C alkanoic acid or a halogenated derivative,

  such as acetic acid or chloroacetic acid).

  Any substitute Ar that is not

  ortho group of the nitrogen-substituted chloroacetylamino group is preferably selected from C 1 -C 4 alkyl groups (for example CH 3),

  halogens (for example Cl, Br) and (C 1 -C 4 alkoxy) groups -

carbonyl (for example C 00 CH 3).

  When Ar contains 2 cyclic heteroatoms, one of them is N and the other is preferably selected from O and S. A preferred subgroup of the compounds of formula is

  by the compounds in which Ar contains either a heteroaryl or a

  cyclic atom (pyrrolyl, thenyl, furarnyl), or 2 neighboring cyclic heteroatoms (isoxazollyl, isothiazolyl, pyrazolyl) The nitrogen-substituted chloroacetylamino group is preferably attached to the cyclic carbon atom in the f-position of the cyclic heteroatom (s); thus, for example in position 3 when Ar is a pyrrole, thiophene or furan ring and in position 4 when Ar is an isoxasole, isothazole or pyrazole ring. A preferred subgroup of this latter group consists of compounds in which the Ar group is is substituted in ortho, preferably in the ortho-ortho position of the nitrogen-substituted acetylamino group, especially when the

  or the substituents are chosisi in the group specified above.

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

  with a C 1 -C 4 alkyl group, especially CH 3 or C 2 H 5 Ar

  It is preferred to use a thiophene, isothiazole or isoxazole ring, especially an isothiazole or thiophene ring. A particularly preferred subgroup of the compounds of formula I are

  compounds in which Ar represents a thiophene ring, in particular

  a 3-thienyl ring at least 254-disubstituted, especially

  3-thienyl compounds in which the substituents in

  2 and 4 are selected from C 1 -C 4 alkyl groups and

C 1 -C 4 alkoxy.

  When Y, R 3, R 4 and R 4 'represent groups

  halogen-substituted hydrocarbons, this halogen is preferably

  Cl or Br; such a substituted hydrocarbon group is more specific

  When Y represents a hydrocarbon group substituted by a halogen, it is generally not preferable

  placed in position 1 when it is intended to be used as a herbicide

  These halogenated compounds in the 1-position are generally unstable, however, they can be used as valuable intermediates for the preparation of other compounds of formula I, for example those in which Y is alkoxyalkyl or pyrazolylmethyl. ; an appropriate example of such a meaning

for Y is 2-Cl-ethyl.

  When Y, R 3, R 4 and / or R 41 represent C 1 -C 8 alkyl, C 3 -C alkenyl or C 3 -C 8 alkynyl groups

3 8 3 8 '

  Preferably, when Y, R 3 R 4 and / or R 41 are cycloalkyl or cycloalkenyl, or contain cycloalkyl or cycloalkenyl, these cyclic hydrocarbon groups preferably contain up to 6 carbon atoms.

of carbon.

  When R 1 represents a C 1 -C 5 alkyl group,

1 15

  It is preferably CH 3 or C 2 H 5, more particularly CH 3.

  The expression "ester or amide function" used with reference to the meaning of Ysl applies to all functions that can be

  by reaction of the COOH group of an acid with an organic compound

  Any suitable reaction with this acid with removal of water, for example an alcohol, an amine, a mercaptan, an oxime: a hydrazine, a hydrazide or a hydrazone. Examples of suitable esters represented by Y 1 are the (alkoxy) groups. C 1 -C 6) -CO, (C 3 -C 5) alkynyl) 0-C 0, etc. As examples of groups

  amide which can be represented by Y 1 are the (alkyl-

  amino C 1 -C 4) -CO, di (C 1 -C 4 alkyl) -amino-CO, CO-NHNH 2 and

C 0 -NH-N = C (C 1 -C 3 alkyl) 2.

  When R 2 represents CH 2, this group can be substituted

  killed by 1 or 2, preferably a C 1 -C 5 alkyl group. When R 2 represents CH 2 CH 2, this group may be substituted with 1, 2, 3 or 4

  C 1 -C 5 alkyl groups, but is preferably mono or di-

  When CH 2 CH 2 is disubstituted, the substituents are

  preferably on different carbon atoms.

  Preferred C 1 -C 5 alkyl substituents for R 2 are CH 3 and C 2 H 5, especially CH 3 when R 2 is substituted

  by C 1 -C 5 allyl groups, it is preferably monosubstituted.

  R 2 is more particularly CH 2 or CH (CH 3).

  When Az represents one of the aromatic heterocycles

  defined above, the cycle may be unsubstituted or substituted

  kill; substituents which are suitable for these meanings of Az are, for example, one or more C 1 -C 5 alkyl groups (such as CH 3, C 2 H 5); these substituted heterocycles are preferably mono- or disubstituted. When Az represents a di or triazole, it is preferably a 1-yrazolyl, 1-imidazolyl, 1,2,3-triazole or

  l-yl or u 2: 4-triazol 1-bye, N-substituted or substituted, in particular

  ## STR2 ## The expression of the present invention can be as follows:

  When Az represents the 5-membered heterocycle connected to R 2 by a cyclic carbon atom defined above,

  this cycle is for example a furyl, chienyl, thiazolyl,

  thiazolyl, oxazolyl, isoxazolyl, i, 2 :, or 1,3,4-thia or oxa-

  diazole or 1,3,4-triazolyl, unsubstituted or substituted, for example by one or two substituents selected from C 1 -C 4 alkylthio C 1 -C 4 alkoxy C 1 -C 4 alkoxy groups as typical examples

1 42 1 4

  such meanings include 2-furyl, 2-thienyl,

  2-CH 3-4-thiazolyl, 3-CH 3-5-isoxazolyl, 2-C 2 H 5-1,3,4-oxadiazole-5-

  Ye, 3-CH 3-1,2,4-oxadiazol-5-yl, 1-CH 3-2-CH 3 S-1 3,4-triazol-5-yl

and 2-CH 3-1,3,4-triazol-5-yl.

3 3

  When Az represents a pyrimidine group, this

  it can be connected by its carbon atom located in position 2, 4 or 5

  at R and is for example a 2-pyrimidinyl group.

  When Az is the bicyclic derivative of 2-oxo-1-pyrrolidone

  lidynyl defined above, the henzo residue may be unsubstituted or substituted, for example with halogens; an appropriate example

  for such a meaning -is the 2-oxo-1,3-benzo group

  thiazol-3-yl and its 4-chloro derivative.

  When R 3 represents the defined hydrocarbon group

  above, this hydrocarbon group may be unsubstituted or substituted

  killed, for example by halogens, cyano groups, an azole group such as 1-pyrazolyl and / or a C 1 -C 4 alkoxy group; these

  substituted hydrocarbon groups represented by R 3 are preferably

  monosubstituted references Examples of such meanings for

  R 3, there will be mentioned CH 2 CH 2 Cl, (1-pyrazolyl) -CH 2 CH 2 CH 2 CNI 3,5-dimethyl-1

  pyrazolyl. The appropriate meanings for A-O-R 3, when A is connected to R 3 to form a ring are, for example,

  1,3-dioxolan-4-yl-C 1 -C 3 alkylene, 1,3-dioxolan-2-yl groups

  C 3 -C 3 alkylene and 2 or 3-tetrahydrofuryl-C 1 -C 3 alkylene.

  When A is not linked to R 3 to form a ring, it is preferably non-aromatic; it is in particular a C 1 -C 8 -alkylene radical separating the oxygen atom and the nitrogen atom to which it is connected by I to 3, preferably 1 or 2 carbon atoms. appropriate for A, we will mention

  CH 2 or CH 12 -CH 2 groups and their monomethylated derivatives, in particular

  CH (CH 3), CH 2 CH 2 and CH (CH 3) CHG 2; R 3 is then more specifically

  C 1 -C 3 alkyl group such as CH 3 C 2 H 5 and nC 3 H 7 A may be unsubstituted or substituted, for example by alkoxy groups. C 1 -C 5 A substituted A group is preferably mono-substituted.

  The invention also includes methods for preparing

  In a first process, the compounds of formula I a) are used starting from a compound of formula II Ar o, 2 E1 in which Ar and Y have the above-mentioned sittion, and replacing the OH group of the N-group. hydroxyacetyl with Cl; b) in another process, reacting a compound of formula III Ar-NH-COCH 2 Cl II wherein Ar has the meanings indicated above, with a compound of formula IV

LY IV

  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 of formula Ia CO-CH Ci Ar N 2 Ia

CH-Y 2

  R 2 R 'wherein R' is H or C 1 -C 3 alkyl, Y 2 is Az ', OR 3, N (i, 3) CO CH 3 and Az' is a di or triazole connected by one of its nitrogen atoms at CER 'and Ar and R have the meanings indicated above, starting from a compound of formula V CO-C Cl Ar N C-CH 2 c V

CH -C 1

R '

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

HY 2 VI

  in which Y 2 has the meanings indicated above,

  (d) another process is to acylate with nitrogen a compound of formula

  wherein Ar and Y have the meanings indicated above, using chloroacetyl chloride or a functional derivative.

reagent of this chloride.

  The process a) according to the invention can be carried out by conventional procedures and under conditions

  known for the substitution of a group O H by a chlorine atom.

  This substitution can be carried out for example by processing

  as a compound of formula II by a chlorinating agent such as thionyl chloride under conditions known per se for

analogous reactions.

  According to a variant of this chlorination process,

  first converts the compounds of formula II into their sulpho

  nyloxylated, for example by sulfonation with oxygen using a

  sulfonyl halide and then converting the sulfonated

  Nyloxylated compounds of formula I sought by substitution

  nucleophile of the sulfonyloxy group by a chlorine atom.

  The reagents providing the IC anions necessary for this nucleophilic substitution are, for example, alkali metal chlorides, such as NaCl, quaternary retrabutyla = onium chloride or 4-dimethylaminopyridine hydrochloride. This substitution is advantageously carried out in CH 2 C 12 or in one

  two-phase hydro-organic system, in which the organic phase

  It consists of, for example, 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 C.

  The process b) can be carried out according to standard procedures, under conditions known for the N-alkylation of the amides. The reaction is advantageously carried out in a solvent which is inert under the reaction conditions, for example dimethoxyethane or acetonitrile or in a two-phase hydro-organic system in the presence of a trans-

live fertility.

  The appropriate meanings of L, in formula IV,

  are CI, Br or the sulphonyloxy radical of a sulpho organic acid

  nique, for example methanesulphonyloxy or p-toluenesulphonyloxy.

  The compounds of formula III are preferably used

  The salts are obtained in the usual manner by reacting the compound of formula III with a base such as an amide, a hydride, a hydroxide or alcoholate

of alkali metal.

  In order to prepare the compounds of formula Ia by process c), the compounds of formula V are advantageously used in the form of

  alkali metal salt, for example sodium salt When Y 2 is a di-

  or triasole, the compound of formula V can also be used at

  the state of N-trialkylsilyl compound, for example N-trimethylsilyl.

  The reaction can be carried out in the usual way -

  The reaction of process d) can also be carried out

  in the usual way, under known conditions for N-chlorine

  acetylation of amines When the agent used for this chloracid-

  tylation is CICOCH 2 C 1, it operates advantageously in the presence of a

  acid-binding agent, for example K 2 C 03.

  The compounds of formula I can be isolated from the mixture

by conventional techniques.

  It will be noted that it is possible to carry out, according to conventional procedures, the mutual conversion of a compound of the invention into another, for example by conversion of an acidic group into an ester group or a carbonyl group. an oxime, a haloalkyl group to an ether group (or vice versa), etc.

  It should also be noted that the compounds of the invention may contain

  one or more centers of asymmetry and may therefore exist enantiomeric, diastereomeric, racemic forms, or

  in geometric isomeric forms In general, in the

  According to the invention, these compounds are used in the form of a mixture, even if the separation can be carried out by

known techniques.

  The compounds corresponding to formulas II, III, V and VII

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

  The compounds of formula II can be obtained by ammonolysis of an ester of the compounds of formula VIII ## STR3 ## in which Ar has the meanings indicated above, with a carboxylic acid, and subsequent introduction of the group Y (as defined above). above) in the compounds of formula VIII by nitrogen alkylation These esters are obtained by acylation of the corresponding compounds of formula IX Ar INH 2 IX wherein Ar has the meanings indicated above, using the ester suitable for PH 0-Ct 2 COC 1, for example using

of CH 3 CO-OCH 2-COC 1.

  The compounds of formula III can also be obtained by acylation of a compound of formula IX with the aid of chloride

chloroacetyl.

  The compounds of formula V (which are in fact a subgroup of the compounds of formula I) can be obtained by reacting a compound of formula IX with a suitable aldehyde to give a Schiff base which is reacted with the chloride

chloroacetyl.

  The compounds of formula VII may be obtained by nitrogen alkylation of a compound of formula IX. This alkylation may be carried out in the usual manner, using the appropriate alkylating agents (for example the halides) or, where appropriate, by reduction passing through the base

Schiff or amide.

  Many of the compounds of formula IX are new.

  A particular group of new compounds of interest

  Formula IX is composed of 3-aminothiophenes substituted at the 2- and 4-positions with groups selected from C 1 -C 4 alkyl and C 4 -C 4 alkoxy (compounds of formula I Xa).

  of formula I Xa are also an object of the invention.

  The compounds of formula IX may be obtained by reduction of the corresponding nitro compounds, for example by

  catalytic hydrogenation under pressure in the presence of palladium.

  Compounds of formula I Xa carrying a CH 3 group in position 2 or 4

  can be obtained by reduction of the corresponding thiophene-carboxylate

  laying with a complex hydride, such as sodium hydride

  and bis (methoxyethoxy) aluminum When appropriate,

  The compounds of Formula I Xa can also be obtained from the corresponding carbamate esters, for example benzyl carbamate, by hydrolysis. The carbamates used as starting materials can be obtained, for example, from the corresponding acids via their azides. following with a Curtius reaction. When the preparation of a starting material 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 known methods.

  The compounds of formula I have utility because they

  allow to act on the growth of the plants or to modify it.

  Seeds undergoing germination are referred to as plants.

  planted shoots and established vegetation, including

including the underground parts.

  In particular, the compounds according to the invention can be used as herbicides, as shown, inter alia, by the damage caused to monocotyledonous as well as dicotyledonous plants, such as Lepidium sativum Avena sativa Agrostis alba and Lolium perenne in tests with doses corresponding to an application rate of 1.4 to -5.6 kg / ha applied pre or post-emergence Because of their herbicidal activity, the compounds according to the invention can be used to combat the bad dicotyledonous herbs and grasses, as shown by other tests conducted with representative compounds at doses corresponding to an application rate of 0.2 to 5.0 kg of active ingredient, eg 0.2, 1.0 and 5.0 kg active ingredient per hectare on dicotyledonous weeds, such as Amaranthus retroflexus Capsella bursa-pasoris, Chenop odiur alba Stellaria media, Senecio vulgaris and Galium aparine, and especially the bad ones grasses, such as Aro repns Agrostis alba Alopecurus myosuroides, Apera spica-2 eti, Arena fat Echinochloa crus-galli,

  Bromus tectorum, Sorghum halepense Di $ itaria spp and Setaria sp.

  Other tests indicate favorable persistence in the soil of

compounds of the invention.

  The compounds according to the invention are relatively

  less toxic to crops than to weeds.

  Among others, there is a selective herbicidal activity on maize, soybean, cotton, sugar beet, potato, alfalfa, sunflower, rapeseed, peanut or flax, according to

  nature of the compound and the application rate Compounds according to

  vention can therefore be used as selective herbicides

in places of culture.

  The invention therefore also comprises a method for combating weeds, preferably in

  particularly in a place of culture such as

  above, which consists in applying on the premises a

  effective herbicidal amount (a selective herbicidal

  In a particularly preferred embodiment of the invention, a compound of formula I is used in pre-emergence (both from the cultivated plant and from the plants). weeds) to selectively control weeds in growing areas. For the general herbicidal application as for the selective herbicidal application of the compounds according to the invention, the quantity to be applied to achieve the desired effect varies according to the nature of the crop grown 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

  and similar factors Doses of appropriate applications

  may be detained by routine techniques well

  specialists, or by comparing the activity of the compounds

  According to the invention, reference products are known for which the application rate is known by example in greenhouse experiments. However, in general, satisfactory results are usually obtained by applying the compound at a dose in the range of about 0.1 at 5 kg / ha, preferably about 0.2-4 kg / ha, more preferably

  from 0.5 to 3.0 kg / ha, repeating the application when it is necessary

  When the application is made in places of culture,

  the application rate will preferably not exceed 3 kg / ha.

  The compounds of formula I can be and are preferably used in the form of herbicidal compositions in the form of

  combination with one or more acceptable diluents for this

  The appropriate fractions 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 or liquid diluents. it is advantageous to work with higher proportions of surfactants relative to the active ingredient; this is achieved by incorporating an agent complement

  surfactant in the formulation or in the tank.

  The forms ready for application generally comprise from 0.01 to 25% by weight of active material. Naturally, the active ingredient contents may be lower or higher depending on the intended application and the physical properties of the compound.

  concentrated forms of the products, designed to be diluted before use

  usually contain from 2 to 90%, preferably from 10 to

% by weight of active ingredient.

  Among the useful formulations containing the compounds according to the invention, fine powders, granules, granules, concentrated suspensions, wettable powders, emulsifiable concentrates and the like will be obtained in the usual manner, for example by mixing the compounds according to the invention. The invention with the diluents More specifically, the compositions are obtained by mixing the components, the fine solid compositions by mixing and usually brocating, the 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 microenca-sulated form.

  In the herbicidal products, additives can also be introduced to improve the results obtained with the active ingredient and to reduce foaming, caking and drying. corrosion The term "surfactant" as used in this application applies to substances acceptable for use in herbicide products and which

  confer properties of sedation,

  dispersibility or other properties affecting the state of

  As examples of surfactants, mention may be made of lignin-

  sodium sulfonate and sodium lauryloilfate.

  The term diluent, as used in this application, refers to a liquid or solid material acceptable for use in herbicidal products and which serves to dilute a concentrated material to the desired concentration.

  or suitable for use For fine powders or granules

  nules, it may be for example talc, kaolin or diatomaceous earth; for the liquid concentrated forms, it may be for example a hydrocarbon, such as xylene, or an alcohol, such as isopropanol, and for the liquid forms of application, between

other water or diesel.

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

fungicide or insecticide.

  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 indicated.

* EXAMPLES

  First, examples of composi-

herbicides.

  EXAMPLE A: Wettable powder 25 parts of a compound of formula 1 are mixed with

  Compound Example 25 below, with 25 parts of synthetic silica

  tick, 2 parts of sodium lauryl sulphate, 3 parts of lignin-

  Sodium sulfonate and 45 parts of fine kaolin and milled to an average particle size of about 5 microns A wettable powder is obtained which is diluted with water before being used

  in the form of a spray liquor at the desired concentration.

  EXAMPLE B Emulsifiable Concentrate 20 parts of a compound of formula I, for example compound 25 hereinafter, 40 parts of xylene, 30 parts of dimethylformamide and 10 parts of dimethylformamide, are carefully mixed until a homogeneous solution is obtained. an emulsifying agent (for example the commercial product ATLOX 4851 B, a mixture of a calcium alkyl aryl sulphonate

  and a polyethoxylated triglyceride from Atlas Chemie Gmbh).

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

  lisation. EXAMPLE C Granules 5 kg of a compound of formula 1, for example compound 25 below, are dissolved in 25 liters of methylene chloride. The solution is then added to 95 kg of granular attapulgite (at

  a particle size of 0.30 to 0.70 mm) and mixed carefully.

  The solvent is then evaporated under vacuum.

  The examples which follow describe the preparation of the compounds according to the invention; in these examples, the temperatures are indicated in e C, the pressures in mra Hg and the values of Rf have

  were obtained on silica gel, unless otherwise indicated.

FINAL COMPOUNDS

EXE-PLE 1

  N- (224-dimethyl-3-yl) -N-1 (3: -dioxolan-2-ylmethyl) -chlor-

  (a) A mixture of N- (2,4-dimethyl-3-yl) -N- (1,3-dioxolan-2-ylmethyl) -hydroxyacetamide, 1.7 g (0.0063 mole), of benzyltriethylammonium chloride, 7 ml of toluene and 7 ml of

  30% sodium hydroxide solution is added dropwise under good stirring.

  under cooling, 1.31 g (0.0069 mol) of p-toluene chloride were

  sulfonyl in 3.5 ml of toluene When the heat generated by the reaction has subsided, stirring is continued

  for another 20 hours at room temperature.

  The toluene layer is separated, washed with water

  and dried over anhydrous Na 2 SO 4.

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

  N- (2,4-dimethyl-thien-3-yl) -N- (1,3-dioxolan-2-) is obtained.

  ylmethyl) -toluene-sulfonyloxyacetamide ("tosylate") melting at

O'-103.

  A mixture of 2.16 g (0.0051 mol) of this tosylate, 1.84 g (0.0066 mol), is heated at 90 ° C. for 6 hours with stirring.

  of tetrabutylammonium chloride, 8 ml of water and 16 ml of toluene.

  The toluene layer is then separated, dried over Na 2 SO 4 and evaporated in vacuo. The residue is chromatographed on a silica gel column. The elution with hexane / ethyl acetate 2: 1 gives the title compound. in the form of

  crystals of analytical purity melting at 76-78.

EXAMPLE 2

  N- (24-dimethylthien-3-yl) -N-methoxethyl-choracetamide (Erocédé a)

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

  dimethyl-thien-3-yl) -N-methoxyethyl-hydroxylacetamide and 0.92 g (0.008 mole) of 4-dimethylaminopyridine (= DMAP) in 80 ml of dry methylene chloride are added with stirring under cooling. g (0.008 mol) of methanesulfonyl chloride in 20 ml of dry CH 2 C 12. The mixture obtained containing the DMAP hydrochloride and the methanesulfonate of the starting compound is heated to reflux.

  for 25 h and then evaporated under vacuum.

  The residual oil, after chromatography on a

  column of silica gel (elution with ethyl ether) solidifies

  refrigerated at -20; the product then melts at 54-55.

EXAMPLE 3

  Ethyl ester of N-chloroacetyl-N: -2-carbomethoxy-4-methyl-

  Method 1 b) A suspension of 1.5 g (0.05 mole) of sodium hydride (80% dispersion in mineral oil in 250 ml of sodium bicarbonate).

  Dry dimethoxyethane (= DME) is added in portions, under good agitation.

  9.9 g (0.04 mol) of N- (2-carbomethoxy-4-methyl-3-yl) -

solid chloroacetamide.

  When the addition is complete, the solution of the sodium salt is stirred for another hour at 50, then allowed to come to room temperature and treated with a solution of 7> 25 g.

  (0.04 mol) 2-brominopropionate ethyl in 50 ml dry DIE.

  After 4 hours of reaction at 50, the mixture is filtered and evaporated under vacuum (50 / 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 tube distillation at

  balls; the desired compound is obtained in a state of analytic purity.

  tick, boiling at 135 C / O, 005 mm Hg.

EXAMPLE 4

  N-l-yao lehl Ng "-iehltin ylchl oracetamide & rocédé b)

  To a mixture of 19.35 g (0.095 mole) of N- (2,4-dimethyl)

  thien-3-yl) -chloroacetamide, 4.15 g (0.01 mole) of benzyl chloride

  dimethyl hexadecylammonium, 40 g (1 mole) of sodium hydroxide, ml of methylene chloride and 40 ml of water are added with good stirring 17 g (0.11 mole) of hydrochloride of 1-chloromethyl- pyrazole

  solid at such a rate that the temperature does not exceed 25.

  When the addition is complete, shake for

  2.5 hours at room temperature. Another 100 ml of water are added.

  The organic layer is separated off, washed with three portions of 200 ml of water, dried over Na 2 SO 4 and evaporated to dryness. The residue is chromatographed on a column of silica gel. Elution with hexane / ether mixture Ethyl 11 gives the title compound as a syrup of analytical purity which crystallizes overnight at -20; the product then melts at 88-89 (after recrystallization from ethyl ether)

EXE: ILE 5

  Ethyl ester of N- (chloroacetyl-1-N-3-di-35-dimethyl-isoxazol-4-yl)

alanine (2 b)

  9.4 g (0.05 mole) of N-

  isopropyl-4-lH-loperazide in 150 ml of dry acetonitrile (= CH 3 CN) with good stirring to a suspension of 1.8 g (0.06 mol) of sodium hydride (80% dispersion). in mineral oil) in

half of dry acetonitrile.

  When the exothermic reaction (34) has subsided, the sodium salt solution is allowed to come to room temperature,

  then treated with 9.05 g (0.05 mole) of 2-bromine

  ethyl propionate in 25 ml of dry acetonitrile.

  When the addition is complete, the reaction mixture is heated at 500 for 3 h, then evaporated to dry.

  the residue in 100 ml of ethyl ether and the residual oil is filtered off.

  duel obtained by evaporation of the filtrate is chromatographed on

  a column of silica gel Elution by the mixture of ethyl ether

  lique / hexane 1: 1 gives the desired compound melting at 49-50.

EXAMPLE 6

  N-L-1 H-Eyrazol-el 4-methyl-th th -acetamide (method c)

  To a solution of 12.7 g (0.1 mol) 2,4-dimethyl-

  3-amino-thiophene in 100 ml of dry benzene containing 16 g of 3 A molecular sieve and two drops of concentrated H 2504, 8.5 ml (015 mole) of acetaldehyde are added dropwise with stirring.

  the temperature does not exceed 25.

  When the addition is complete, stir the mixture

  reaction for another 24 h at room temperature, and then filtered.

  Removal of the solvent gives the Schiff base as a liquid

light brown.

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

  to -9.9 g (0.086 moles) of chloroacetyl chloride.

  When the addition is complete, the reaction solution is stirred for a further 30 minutes.

  drop at the same temperature with 12 g (0.085 mol) of 1-trimethyl-

  When the addition is complete, the acetone / dry ice bath is removed, the mixture is allowed to come to room temperature and the mixture is stirred for a further 20 hours. The reaction mixture is filtered and evaporated in vacuo. residual syrup on a column of silica gel Elution with hexane / ethyl ether 3: 2 gives colorless crystals of the title compound, which melt at room temperature.

  76-78 after recrystallization from ethyl ether.

EXAMPLE 7

  U: -g 4-L-thethox-2-yl L-t-iene-3 (1) N 2 -ethoxethe thiazol) chioracetanide (method d)

  To a mixture of 6.05 g (0:03 mol) of MN- (2-ethoxyethyl) -

  4-methoxy-2-methyl-3-amino-thiophene, 4.15 g (0.03 mol) of K 2 C 03,

  10 ml of water and 100 ml of CH 2 C 1 are added dropwise under stirring.

  without cooling, the solution of 3.4 g (0.03 mol) of chloride

  of chloroacetyl in 10 ml of CH 2 C 12 When the reaction e Tother-

  (250) calmed down, continued stirring for 4 hours at

ambient temperature.

  The methylene chloride layer is then separated, washed twice with 100 ml of water, dried over Na2O4 and evaporated in vacuo. The crude title compound obtained has the analytical purity;

  Rf = 0.23 (hexane, ethyl ether, 1: 2). A small portion was

  of the bulb-tube distillation substance: the product

tip at 168-170 / 0.05 mm Hg.

  The compounds of formula I identified below have been obtained by one or more of the procedures described in

  Examples 1 to 7 above (M Ie represents CH and Et C H 2).

3 2 D

TABLE A

Comnose n,

1 4 -,

  Aryl L Characterization le-thien-3-yl CH 2 oc 2 H Ir:

CH 2 CH 20 CH 3

P. ' 25-260

  Rf = O-, 45 (cyclohexia / ethyl acetate 1: 1) Rf = 0.3 (cycloalkyl / ethyl acetate 6: 4) -510 -960 =, n 115479 -610 -A 6 th

F 145 1480

F 48-490

= 1.5345

  D 188 12 l / 0, 005 mm lîg F 77-79 c 'n 204,5342 D n 1) 5192

F 82 84

F 135 13 V '

F 1410

F 89-890

  F 76-7 uo 3 2-i-th-thien-3-yl CH CH GCH

2 2 3

7

1 1

12

1 3 1 C li i 5 1 6

1 7

1 8 1 9

2,4-di Me-thiene-3-

  He He He He He He He He He He He He He He He He He He He He He He He He He He There It He. 4 1 3

C 2 H 5

ic 3 47 CH 2 -Cl, '= C Fi 2

M C (CI-1% = C 4

2 31 2

CH 2- C (CH

3) 2-C = CH

  CH 2 C 6 p 5 Cil 2 CF 3 CH-C (Cl'i = CH Cyl 2-C (Br) = CH 2

CH 2 COO 4.

CH 2 COOM 2

  ## STR5 ## ## STR2 ## ## STR2 ## where ## STR2 ##

CH 2 3) 2

Colossal CH Jl i

2 U 3 17

  CH 2 neck H zec (eyelash 3) 2 jicj Ckl # 2 - ('- Py razol' -%

CIMM 4 1 1

3) (1-pyrazolvie) 7-01 yl e-1)

22

2 4 dr.

2 7

  143-1 fi 40 T A B L R A U A (continued 1)

253063-1

Compound no

? Ỉ 2,

  2 9 33 36 41 -> 4-di Me Characterization Aryl-thien-3-yl% r "p, (CH There, CH

2q.

CH (CH 3) -

CH N

2 / ii - - - Me CH rh

CH (Me) -

  CH (2-juryl) CH (2-thienyl) CH 2 U

3-M e i soxazole-5-yi-

CH 2 N CH 2 O c P = Me H 1 N 2-O '

F 132-1330

78-790

57-59 66-67

71,780

F. F. F. F.

F '04 -560

F 71-720

  ## EQU1 ##

F 110-115-

11-1-1

  C HIRI-I H NI -N 2 HZ-12, N 1111 I Sl Ie Me

F 119-1250

F 'to 20-122 "

itil NID

CH /

2 1 m

F 68-700 '

  46 CH 2 CIL 2 H CH 2 O and I 79-80 E 115/0, 001 mm Hg

-80

n D = 1.5 c

E 110-111 '/ 0.001 MMH 9

P 48-500

F 55-570

F '54-55

E.110 '/ 0.01 mm Hg

Rf = 0.36 (ethyl ether)

  1: 1) E 148 -150 '10, 3 mm H Ig, CH 2 OC 3 2 CH 2 O and CH 2 CH 2 oc 3 H 7 n CH (I 'ie) CIl 2 O Mc

% CH

C ("e) 2" CH or CH 2 O 55

F 76-780

  ## STR3 ## Compound No. Characterization Aryl and 2,4-di-thien-3-yl 60 CH (b ') ECH 2 CH 2 ci

C11 (O% ie) CH 01 1 e.

  CH 2 OCH 2 CH 2 C,% Ie CH (- '' e) OC-4, CH CN

CH 20 C lu, 2 r -

  CH (1IL) OC CH (Me) CH 2 CH (Me) CH 2 CH = N

F 62-640

Rf = 0.3 (ethyl ether

  lique / hexane, 1: 1) t.n 7-J 8 "/ 0.005 mm Hg

P 59-640

mp = 0.31 (hexane / acetone)

ethyl acetate, 3: 2)

Pf = 0.23 (hexane / acetone)

ethyl acetate, 4: 1)

F 76-78 "

F 57,590

P 68-70c,

Rf = 0.4 (E xxiine / a-c-e)

  tate d 1 dehyle, 4: 1) 64 he he he he el he

6.3

72 75 he he the

CH 2 C H = NO E ,,

  CH 2 VI 2-C (11 e, = 1 NO-0 C 4.2-C ('rie) = No And CH (Mi, e) CH (1-12) N (12 le) COMC

2-the e-4-And-thiène-

3-yle es He

2-and-4-Me-thiène-

  3-yl CH (Me) CH 2 omega CH 2 O and pyra 7-olyl -1 CM 2 CH oc H, 2 2 O CH (1 vle) Cil'20 e ie pyrazolyl -1-CH

CH r

2-01-t E 14 2 -144 '/ O, 2 mm Hg

F 49-500

F 53-540

Rf = 0 47 (ether ther

liqu / hexane, 7: 3)

Rf = O 47 (ethyl ether)

liquefied / hexane, 7: 3) F 63e-51,

: 1 5242

n, n D = 1.5328

2,4-di Et-thiene-3-

  Y le il T A B L E A U A (continued 4) Aryle

2-i C il -4-; c?

  3 7 3-yl e 4-OH-2-1-e-tiene 3-yl

2-1 'e-4-1-IC-O-thene-

  3-yl compound no y Characterization pyrazolyl-1-CH 2 85

CH (le) CH 2 ci'-i, -

  pyrazolyl-1H 2 CH 2 -O and CH 2 CH 2 O and F 90-92

F 24 O

E.168-170 '/ 0.05 = Hg

F 44-460

  E.180 * / 0.001 mm Hg E.135 "/ 0.001 mm Hg E.148-150 '/ 0.001 mm Hg

F 1000 -

  F 37-38 e 'I; YI: F 89-9' l, ant-to: F 75-762

87 2-Me-4-And O-thiene-

3-yl pyrazolyl-1-CH 2

* 88 2-Me-4-i-C 3 H 7-

  thien-3-yl 89 2-dl-4-n C 4 H 90 thien-3-yl CH 2 O And

2-Me-4 O CF 2 C 4 = Ct'2-

  thien-3-yl pyraVlyl-1-PH 2 thien-3-yl 92 2-Me OH-4-, MeOH hiene-: -yl

93 2-11, e S-4-1 'e-tiien-

  3-yl 94 5 96 to 97 to 97 b 12 O and Ci 12 CH 2 ome

2-M-s (O) thene

3-yl 042 O E t.

2-1-W; O -4 -K thiene-

2 - 3-yl e Cpt 2 L t

thiène-

3-Y He CH O And

thiene -

  3-yl pyl-V zolyl-1-yl 2-thien-3-yl pyr-pzelyl-1Cl 2 2 Mie C-thien-3-life CI,

2 53 06 '3 1

TABLE A (continued 5) Aryl y Ci

2 Mec (= N 10 I-10) 4-Me-

thien-3-yl pyrazolyl-1-CH S '

? -Me C (C Et) 2 -4-Me-

thiene-3-yl CH 2 O And

2-1-Ile 4-0 thiene-

3-yl CH (Me) CH 2 O Me

2-COO "e-4-Me-thiène-

  3-yl CH 2 C = CHF CHF (CH 2) CH (m), CH 2 Cl 2 C 7 O 4 O 5 Mn, e-thien-3-yl pyrazolyl-1-CH 3 -hene-3-yl CH 2 o And n 'CH CODC H in

2 3 7

pyrazo 1 yl-1-CH n

2,4-di Me-5-Cl-

  thien-3-yl, CH 2 o And n CH O IP CH OCH n

2 2 2 3

  T o rt hy d ro f Li ry i 2 -R CH 2 4 r w Composd 1 no

102

1 105

'109

to 110 b Ili

113

1 It is the characterization

F 123 '

46 to 4.70

-220 "/ 0.005 mm Hg

1; 5273

D

= 1.5112

D = 1 D

= 1, 5412

D

D = 1 '5321

  ## STR5 ## ethyl acetate, 7: 3) -e = O, 38 (cyclohexane / ethyl acetate -, - 6: 4)

68-739

-77 "14 oo / ooo 5 mm Hg

(ethyl ether

  3-pyrazolyl-1-CH 2 CH 2 O and pyra-, olyl-1-CH 2 CH 2 O and CH 2 O and

2.5 di Br-4-Ille-

thien-3-yl

2-Me 5 B r-

thien-3-yl

2,4 di 1 1 e 5 C 00 ille-

thien-3-yl

2, 4 di 1, m furan

3-yl -

  T A B L E A U A (cont. 6) Compound No. 1 1 1 O

1-1 7

  Characterization Aryl y 2 4-d LN 1 e-furan 3 CH C'P "e

yie 2 -2 v '-

And CH k, -

2- lily

121

  CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2

1 2,4-tert-1 pyrrole

3-yl And h q

2 1 C O O And> L 3.5 tri -

ftlepyrrole-4-yl n? .4 = 1.55422

D -

pyrazol-1-C "

1 25 3.5 di Me-i soxa'zolqe-

  ## STR2 ## ## STR2 ##

F 49-500

F -45-4101,

  E.1180 / 0.001 mm Hg E.107-108 / 0.001 mm Hg n D = 1.4908

129

And And

3,5-diisoxazole

-1 4-Y the And

132 3,5 di sothi a-

  Re-zo I yl 1 CH 2 Or It CH 2 CH 2 Omey pyrazolyl-1-CH 2 Cly 2 C- = CH

M 2 CH 2

F 43-451,

% J he

F. 109-114 "

F 109-112-

FI 111-1130

136 E I -O-pyra-

zole-4-yl

137 1

  zole-4-yl CH 2 o And E.130 "/ 0.001 mm Hg T A B L E A U A (cont'd 7) Aryl

1,3,3-tri: e-prac-

  Z Ole-4-yl There Is Characterization CH 2 CH 20 'e CH 2 -OC 31 H 7 n And

CH 2-C-CH

pyrazolyl Cu

F 66-67

E 135 / 0.001 mm Hg

F 80-82

F 115-i 17 o

F 96-97

143 1-ie-3, from Et-pyra-

zole-4-yl I,

1 3-die-5-And O-.

  pyrazo-4-yl CH 2 -OC 3 H 7 n CH 2 CH 20 CH 2 O and = n = 1.5008 E 130/0, 001 mm Hg F.

54-56

Intermediate products.

EXAMPLE 8

  methyl imethyl-4-anino-ithophene-2-carboxylate.

  A solution of 45.2 g (0.21 mol) of methyl 3,5-dimethyl-4-nitrothiophene-2-carboxylate in 1000 ml of methanol is hydrogenated for 2 hours under a pressure of 10 bar in the presence of

  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 state of analytical purity, melting

at 88-89 -

EXAMPLE 9

24-dimethyl-3-aminothlothene.

  To 890 ml (3 moles) of sodium hydride and bis- (2-

  methoxyethoxy) aluminum (70% solution in toluene) and 600 ml of dry toluene are added dropwise with vigorous stirring

  a solution of 100 g (0.58 mol) of 3-amino-4-methyl-thiophene-2

  Compound -no methyl carboxylate in 700 ml dry toluene at a rate

  such that the temperature does not exceed 55.

  When the addition is complete, the agitation is continued.

  for another 30 minutes, then the reaction mixture is carefully added in small portions, at 0, to 1200 ml of a solution.

20% potassium hydroxide.

  The toluene layer is separated, dried over MgSO 4, and evaporated in vacuo. The residual brown liquid is distilled under vacuum; the desired compound is obtained in the state of analytical purity

boiling at 49-52 / 0.01 mm Hg.

EXAMPLE 10

  4-methox-2-methyl-3-amino-thioheene The mixture is refluxed for 2 hours with good stirring

  a mixture of 55.4 g (0.2 moles) of N- (4-methoxy-2-methyl-3-thiene)

  benzyl carbamate, 40 g (0.7 mole) of KOH, 600 ml of ethanol and 120 ml of water. The solution is evaporated under vacuum and the residue is diluted with 500 ml of water. light yellow, which separates in 400 ml of ethyl ether and the aqueous phase is extracted

once per 400 ml of ether.

  The combined ether solutions are dried over Na 2 O 4 and filtered. A slow stream of dry HC 1 is passed through the filtrate for 30 minutes with intermittent cooling.

  in an ice bath that the temperature does not exceed 10.

  The hydrochloride of the desired compound which precipitates,

  bottom at 230 (free base melts at 61-63).

EXAMPLE 11

  2-Methylthio-4-methyl-3-amylothiophene 6 g (0.22 atom atoms) of aluminum amalgam

  prepared in approximately 2 minutes at 18.9 g (0.1 mole) of 2-methyl-

  thio-4-mithyl-3-nitrothiophene dissolved in 200 ml of ethyl ether

  The vigorous reaction under control is maintained under control.

  fires in 5 to 10 minutes while cooling the balloon in the ice.

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

6 g of amalgamated aluminum.

  The reaction mixture is then refluxed at moderate reflux

  for 2 hours; during this period, the formation of thiophene-

  The organic phase is decanted and the residue is washed with two portions of 50 ml of ethyl ether.

  combined ether solutions over Mg SO 4 and evaporated under vacuum.

  The desired compound obtained as a residue in the crude state is distilled under vacuum; it boils at 79-81 / 0.5 mm Hg.

EXAMPLE 12

  Listed below are compounds of formula IX which have been obtained according to one or more of the procedures described

in Examples 8 to 11.

Example 12 1

Example

Example

12.2 12.3 Example 12 4

Example 12

Example 12 6

Example 12 7

Example 12 8

Example 12 9

Example 12

Example 12 11

Example 12 12

Example 12 13

EXAMPLE 13

  1, 3-di-CH 3-5 -O-C 2 H 5-4 -NH 2 -pyrazole (Rf = 0.28, tetrahydrofurate);

  hydrofuran / hexane, 9: 1) 3,5-di-CH 3-4-NH 2 -isothiazole (F 82-84)

  4-C 2 H 5-2-CH 2-3-aminothiophene (Rf = 0.25, ethyl ether)

  lique / hexane, 2: 1) 4-n-butoxy-2-methyl-3-amino-thiophene, F 25; (Rf = 0.25, ethyl ether / hexane, 2: 1) -C 2 H 5 O 3 -CH-4-NH 2-pyrazole (F 81-83) 3,5-di-C 2 H 5 1-CH 3-4-NH 2-pyrazole (E 68-70 / 0.10 mm Hg) 3,5-di-C 2 H 5-4 -NH 2 -isoxazole (Rf = 0.39, ethyl ether) (3-m T 2-4-Me-thien-2-yl) ethanone (F 80-81-) (3-NH 2-4-Et-thien-2-yl) ethanone (F 68) (3NH, -4, 5-dl Me-thien-2-yl) ethanone (F 120,123) 2-Et-4-Me-3-NH 2 thiophene (E 74-76 / 0.01 mm Hg) 2 4-di Et-3- 2H-thiophene NH (Rf = 0.24 (CH 2 C 12) O = 1.5511) 2-Et-4,5-di-3-2-thiophene (= 1 5581) 2-Et-4,5-di Me-3-NH thiophene (n, 1.5581) N: -, 4-dimethyl-3-yl-acetoxyacetamide 12.7 g (0.1 mole) 2,4-dimethyl-3-aminothiophene 13 8 g (0.1 mol) of K 2 C 03 20 ml of water and 150 ml of methylene chloride are added dropwise at room temperature 15 g

  (0.11 mole) acetoxyacetyl chloride.

  When the exothermic reaction has subsided,

  stirring is continued for a further 1 h. The organic layer is evaporated.

  The mixture is washed with water, dried over Mg 504 and evaporated in vacuo.

  The solid residue is treated with hexane; we obtain the compound

  investigated in a state of analytical purity melting at 110-1120.

EXAMPLE 14

  N- (24-dienethyl-thien-3-yl) hydroxylacetamide A moderate stream of ammonia gas is passed for 30 minutes with stirring into a solution of 15.9 g (0.07 mol) of N- (2H). 4-dimethyl-3-yl) acetoxyacetamide in 300 ml of methanol. When the exothermic reaction (40) (moderated by intermittent cooling in cold water) has subsided, stirring is continued for another 30 minutes, then the solution is evaporated to dryness. The solid substance obtained is recrystallized from acetate. ethyl; the desired compound is obtained in the state of

  analytical purity in the form of colorless crystals melting at 85-87.

EXAMPLE 15

  N- (2-ethoxyethyl) -4-methoxy-2-methyl-thionhene-3-amine

  To 70 ml (0.245 moles) of sodium hydride and

  (2-methoxyethox-) aluminum (70% solution in toluene) and 30 ml of dry toluene, a solution is added dropwise with stirring.

  9.4 g (0.041 mole) of N- (4-methoxy-2-methylthien-3-yl) -ethoxy-

  acetamide in 125 ml of dry toluene When the exothermic reaction has subsided, stirring is continued for a further 90 min, then the reaction solution is cautiously added in small portions.

  portions, at -10, to 100 ml of 20% KOH solution.

  The toluene layer is separated and the aqueous phase is extracted twice with 100 ml of toluene.

  toluene solutions combined on Na 2 SO 4 and evaporated under vacuum.

  The light brown liquid obtained as a residue is of analytical purity;

  Rf = 0.32 (hexane / ethyl ether, 1: 2).

EXAMPLE 16

  N-L-methoxymethyl-ethyl-L-4-dimethyl-3-aminothiophene.

  The solution of 6.4 g (0.05 mol) of 2,4-dimethyl-3-amino-thiophene and 5.3 g (0.06 mol) of methoxyacetone in 100 ml of dry toluene was refluxed at reflux. 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 under vacuum The residual crude Schiff base is sufficiently

pure for the next operation.

  9.2 (0.048 mole) of this substance is dissolved in

  ml of dry toluene and added without cooling, with good

  to a solution of 28 ml (0.098 mol) of sodium hydride and bis (2-methoxyethoxy) aluminum (70% solution in toluene) in 15 ml of dry toluene. When the exothermic reaction (44) has subsided, the mixture is stirred for a further 90 minutes, then the reaction solution is carefully added, in small portions, to -10, to 40 ml.

20% KOH solution.

  The toluene layer is then separated, dried over Na 2 SO 4 and evaporated in vacuo. The residual oil, after chromatography on a column of silica gel (elution with hexane / ethyl ether, 3: 1) is distilled under vacuum (at tube

  balls); it boils at 94-95 / 0.01 mm Hg.

EXAMPLE 17

  N 5 -2 th-3-4-oxaddiazol-2-ylmethyl): 2,4-dimethyl-thiophene-3-yl

  amine. A mixture of 12.7 g (0.1 mol) of 2,4-dimethyl-3-arainothiophene, 14.6 g (OC 1 mol) of 2-chloromethyl-5-ethyl-1 is stirred for 20 hours. , 3,4-oxadiazole and 13.8 g (0.1 mole)

  of K 2 CO 3 in 150 ml of dry dimethylformamide (DMR 1).

  It is then cooled to room temperature, the reaction mixture is poured into 400 ml of water and the aqueous DMIF solution is extracted with three 150 ml portions of ethyl ether.

  The combined ether extracts are dried over anhydrous Na 2 SO 4 and evaporated.

  pore under vacuum The residual brown oil is chromatographed on a column of silica gel; elution with hexane / ethyl ether mixture gives the desired compound as a liquid

  orange of analytical purity, Rf = 0.2 (ether / hexane, 1: 1).

EXAMPLE 18

  N-1- (2,4-dimethyl-thien-3-yl) 1H-diazide was stirred for 24 h at room temperature.

  (0.412 moles) N- (2,4-dimethyl-3-thien-3-methyl ether)

  yl) glycine and 42 g (1.3 moles) 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 Na 2 SO 4 and evaporated to dryness; we obtain

  the desired analyte of analytical purity melting at 68-70.

EXAMPLE 19

  N: (2,4-dimethyl-3-yl) -N-methyl-5-mercapto-12: 4-triazole

  A mixture of 15 g (0.075 mol) of N- (2,4-dimethyl-3-yl) glycine hydrazide is refluxed for 4 hours.

  and 5.5 g (0.075 mole) of methyl isothiocyanate in 100 ml of ethanol.

  The reaction mixture is cooled to 10 ° C. and the precipitate is separated.

  pity formed by filtration; we obtain the pure compound melting at

184-187.

EXAMPLE 20

  NOT:-? 24: dimethyl-thiene: 3: yl): U :( 4: L-methyl-5-methyl-l-2,4-l-2,4-methyl-1-yl)

triazol-3-yl-métbyl) -alnine

  To a mixture of 9.5 g (0.037 mole) of N- (2,4-dimethyl)

  thien-3-yl) -N- (4-methyl-5-mercapto-1,2,4-triazol-3-ylmethyl)

  amine, 1.1 g of triethylbenzylammonium chloride in 100 ml of toluene and 30 ml of an aqueous solution of sodium hydroxide at 0, 4.7 g (0.037 mol) of dimethyl sulphate are added. The reaction mixture is stirred at ambient temperature for 5 hours, the organic layer is separated off, washed with three 100 ml portions of water, dried over Na 2 O 4 and evaporated to dryness. The residue was recreated twice in ether; we obtain the desired compound

pure state melting at 92-96.

EXAMPLE 21

  N: (2,4-dimethyl-thien-3-yl) -N- (5-methyl-1-yl) 4-hiadiazole Ie-2-1

byl) -amine

  To 10 g (0.05 mole) of N- (2,4-dimethyl) hydrazide

  thien-3-yl) -glycine in 175 ml of methylene chloride is added dropwise 5.5 g (0.05 mole) of acetic anhydride The mixture is stirred for 1 h at 20 C and evaporated to dryness The oily residue is dissolved in 150 ml of pyridine and 11.1 g (0.05 mol) of phosphorus pentasulfide are added in small portions. During the course of the addition, the temperature reaches 480 ° C. 2 h and stirred at room temperature for another 16 h After evaporation to dryness, the residue is dissolved in methylene chloride and the solution is treated successively with iced water, dilute solution of cold sodium hydroxide

  and water, dried over Na 2 SO 4 and evaporated to dryness.

  tography on a column of silica gel gives the pure compound

  as an oil, Rf = 0.23 (ethyl acetate / hexane, 6: 4).

EXAMPLE 22

  To a solution of 2.2 g (0.055 mole) of NaOH in ml of methanol, 5 g (0.05 mole) of acetamidine hydrochloride are added with stirring 15 min later, 10 g are added (FIG. 0.05 mole) of N- (2,4-dimethyl-3-yl) -glycine hydrazide and the mixture is refluxed for 18 hours. After evaporation to dryness, the residue is treated with sodium chloride. methylene and one

  filters insoluble by-products Chlorine evaporation

  Methylene chloride gives the desired compound melting at 85-87.

EXAMPLE 23

  N- (2,4-dimethyl-3-yl) glycyl ether N 2 - (2,4-dimethyl-3-yl) -hydroxide The mixture is stirred at room temperature for 2 h 7 g (0.035 mole) of N- (2,4-diisopropyl) hydrazide. dimethyl-thien-3-yl) -glycine

  in 50 ml of acetone the desired compound is obtained which crystallizes

  read in pure form by filtration; it melts at 126-128.

EXAMPLE 24

The compounds of formula VII identified below were obtained by one or more of the procedures of Examples 13 to 23 above: Example Ar Y Characterization 24.1 2,4-di-CH 3 -thien-3-yl CH 2 CH 2 -OCH Rf = 0.32 (ethyl ether / hexane, 3: 1) 24 2 "C 2 H Rf = 0.23 (ethyl ether / hexane, 1: 1) 24.3" CH Rf = 0.38 (ether 2 ethyl / hexane,

1: 1)

  24.4 "CH 2 Rf = 0.39 (ethyl ether / hexane, 2: 1 Exc. 24.5 24.6 24.7 24.8 24 9 24.10 24.11

-

24.12 24.13 24.14 24.15 24.16 Ar

2-Cl 3 S-4-cii 3 thiene-3-

yl

1,3,5-tri-CH -pyrazole

4-yl

1-CH 3-3,5-di-C 2-5

pyrazol-4-yl

1,3,5-tri - (- H 3 -pyrazole

4-yl

3-c H 3-5-OC 2 H -pyrazole-

4-yl 2> 4-di-CF 3 thien-c 3-yl

2 He 4-di-C 2 H -thiene-3-

yl

2-CH 3-4-c 21 5 -thiene-3-

yl

2-C 2 H 4 -CH 3-thi-ic-3-

  2,4-di-CH 3 -thene-3-yl Characterization E 36 '/ 0.01 mm Hg E 92-94' / 0.01 mm Hg Rf = 0.38 (acetone / hexane, 4: 6) Rf = 0.2 (ethyl acetate-CH OH, 2: 1) Rf = 0.25 (ethyl acetate-CH 3 OH, 9: 1)

Rf = 0.48 (ethyl ether)

lic)

Rf = 0.57 (ethyl ether)

  D = 1.4786 n D = 1.5238 E 98-100 '/ 0.09 mm Hg Rf = 0.52 (ether / hexane, 7: 3)

Rf = 0.55 (ethyl ether)

lique / hexane, 1: 1) y CH r OCH

2 'H 2 3

go he

C 2 H 5

CH CF "eye

2 2 3

  CH 2 cq 2 o C 2 H 5 CH 2 CH 2 oc 3 H 7-n

CH 2 CF 3

CH 2 CH 2 OCH 3

- 'CH 3

OCH

CH-_OE 2 3

CCH 3

___CH 2 OC "13

CH

CHC C CH

N enir

% '"2 __ 3

24 17

He 24.18 VI 1 8

CH, N

2 CH

F_. cil ,, O CH 2 Co Nr (CH 3) 2

CH 2 COOCH 3

  24.19 Rf = 0.15 (CH 2) 2 n = 1.5579 D E.82-87 '/ 0.005 mm Hg 1 1 and 24.20 24.21

EXAMPLE 25

  N- (2-methoxycarbonyl) -3,5-dimethyl-thiene-4-yl) -chloroacetamide

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

  Methyl thiophene-2-carboxylate, 9.1 g (0.066 mole) of C03, 25 ml of water and 150 ml of methylene chloride, 7.5 g (0.066 mole) of chloroacetyl chloride are added without cooling. the exothermic reaction (36) calmed down, stirred for a further 1 hour, then the layer was separated.

  organic, washed with water and dried over Na 2 SO 4 anhydrous.

  The removal of the solvent gives the desired product in the form of

  colorless crystals melting at 157-1580.

EXAMPLE 26

  N - (-Choro 3,5-dimethyl-1He-4 Xl) -chloroacetamide

  To a solution of 5.0 g (0.0245 mol) of N- (2,4-

  dimethyl-3-yl) -chloroacetamide in 50 ml of dry CH 2 C 2 is added dropwise, with stirring, to 00.3.3 g (0.0245 mol) of sulfuryl chloride. After the end of After the addition, the reaction mixture was allowed to warm to room temperature and stirred for a further 20 h. The solvent was then removed in vacuo and the crystalline residue triturated with hexane; we obtain the compound

  investigated in a state of analytical purity melting at 1660 (decomposed

  tion). EXAMPLE 27 N: L-2-1-dietho-xf) ethyl-4-methylthien-3-chloroacetamide

  15 g (0.065 mole) of N- (2-acetyl-4-

  Methyl-3-yl) -chloroacetamide in a mixture brought to 50 of 60 g of dry ethyl alcohol, 60 g of triethyl orthoformate

and 7 drops of concentrated HCl.

  After standing for 30 h at room temperature, the reaction mixture is evaporated under vacuum (50 / 0.01 mm Hg) and the residual brown syrup is chromatographed on a column of silica gel. Elution with hexane / ethyl ether mixture 2: 1: gives the title compound as a colorless, colorless crystal

at 57-58.

EEMPLE 28

  U-L: (I: thoxirino) ethyl: 4: methyl: thiene: 3: -yl: 12-chloroacetamide. The solution is refluxed for 7 hours.

  1.5 g (0.0065 moles) of N- (2-acetyl-4-xylethyl-3-yl) -chlorine

  acetanamide and 6.6 g (0.14 mol) of methoxyanmine in 50 ml of

  dry toluene containing 5 g of MA molecular sieve.

  The color reaction solution is then filtered and evaporated to dryness. The crude syn / anti isomer mixture obtained is chromatographed with a mixture of

  hexane / ethyl ether as a mobile phase.

  First, 0.6 g of a pure isomer (syn isomer) melting at 101-102 ° (Rf = 0.33, hexane / ether, 1: 1) is eluted. The further elution of the silica gel column gives the other isomer

  anti, of analytical purity (0.4 g) melting at 87-89 e (Rf = 0.21).

EXAMPLE 29

  The compounds of formula III identified hereinafter were obtained by one or more of the procedures of Examples 25 to 28. EXAMPLE Ar Characterization 29 1 2-COOCH 3-4-CH 3 -tlhien-3-yl F 118-119 o 29.2 -2CH 3 S-4-CH 13thien-3-yl F 105-106 29.3 2, 4-di-CH 3 -thien-3-yl P 128-1290 29.4 3 5-di-CH -isoxazol-4-yl F 96-980 29 5 3, 5-Di-C 2 H -Ixaz 14 F 669 29 6 4-CH 3 -thien-3-yl F 93-96 e 29.7 2-CH -4-c H-3-thiene yle P 1140

3 25

  29.8 2-CH 4-OCH -thien-1-yl P 14441450

3 3

  29.9 2,4-di-CH 3 -furan-3-yl F 95-970 2-9 10 3,5-di-H-isothiazol-4-yl F 104 1060 29 11 3-CH-5-OF przll 125-1270 3 02 5-przl 1 29.12 2-C 00 C 25-Z, 3,5-tri-CH -pyrrole-4-yl F 163-1650 3 29.14 2,4-di-C 2 H-thien-3-yl F 145 29-1 -CC 34 CH 3thèe25 F 10 29 15 2-CO CH -4-OCH nthien-3-yl F 1291300

3 49

  29.17 2-C 2 U 5 -4,5-di-CH 3 -thien-3-yl F 147-148 o

EXAMPLE 30

  N :( 2-4: dimethyl-1-thien-3 -) -N-methoxethyl-hydroxyacetamide

  18.4 g (0.1 mole) of N- (2,4-di-

  methyl-thien-3-yl) -hydroxyacetamide in 50 ml of dry dimethylformamide (DF) with good stirring to a suspension of 3.0 g (0.1 mol) of sodium hydride (80% dispersion in mineral oil) in

ml of dry DMF.

  When the exothermic reaction (50) has subsided, the solution of the sodium salt is allowed to return to ambient temperature and then treated with a solution of 10.4 g (0.11 mol) of methyl and 2-chloroethyl ether. in 20 ml of dry DMF After the end of the addition, the mixture is heated at 1000 for 4 h and then evaporated.

to see (400/0 01 mm Hg).

  The residue is taken up in 200 ml of ethyl ether,

  washed with 250 ml of water, dried (MgSO 4) and filtered the residual oil.

  The dual elution obtained on evaporation of the filtrate is chromatographed on a silica gel column. Elution with ether gives the desired product in the form of a viscous liquid of analytical purity.

(Rf = 0.25, ether).

EXAMPLE 31

  The compounds of formula II below for which Ar is

  2,4-dimethylthien-3-yl were obtained by the method of

of Example 30.

  Example n Y Characterization 31 1 CH 21 CH = NOCH 3 Rf = 0.21 (hexane / ethyl acetate, 3: 2)

31.2 CH CH = NOC 2 H 5

  31.2 2 H 5 CH = NOC HRf-0.25 (hexane / ethyl acetate, 3: 2)

31.3 CH 2 NOCH F 69-71

  CH 3 31.4 CH 2-C = NOC 2 H Rf = 0.27 (hexane / ethyl acetate 3: 2)

CH 3

  31.5 CHCIIH-i To CH Rf-0.31 (hexane / ethyl acetate, 3: 2) CH 3 31.6 CHCH = NOC 2 H 5 Rf = 0.3 (hexane / ethyl acetate, 3: 2) CH 3 31 7 CH 21 / Rf = 0.12 (hexane / ethyl acetate, 3: 2) C 2

EXAMPLE 32

  N- (4-methoxy X-2-methyl: thiene: -3-yl) ethoxvacetamnide

  To 9.8 g (0.068 mole) of 4-i-ethoxry-2-methyl-3-aminopropyl

  thiophene, 9.45 g (0.068 mol) of C, 35 ml of water and 100 ml of CH 2 Cl 2, a solution of 8.4 g (0.069 mol) of ethoxy-yacetyl chloride is added without cooling. 20 ril of CH Ci

1 2 2 V

  When the reaction is complete, the mixture is stirred for a further 1 hour. The organic layer is then separated, washed twice with 150 ml of water and dried over Na 2 O 4.

Anhydrous.

  The residue obtained at evaporation of the solvent on evaporation

  The rotary die is chromatographed on a silica gel column. Elution with 1: 1 ethyl hexanelether gives

  the objective compound of analytical purity melting at 40-410.

EXMIPLE 33

  The amides of formula Ar NHCOY 3 below were obtained

  by a procedure similar to that of Example 34.

  Example Ar y 3 Characterization No. 331 1 2,4-di-CH 3 -thien-3-yl d 1 H 2 -O 1 H 3 F 62-63 a 33.2 "-CH 3 P 168-169 e

33.3 "-F 140-1420

33.4 "J F 164-1650

  33.5 1,3,5-tri-CH 3 -pyrazol-4-yl -CH 2 011 3 F 85-87 o 33 6 1-CH -3,5di-CH -pyrazol-4-yl "if 200.0 m H 33.7 3-CH 3-5-OC 2 H 5 ç-pyrazole-4-yl -CH 2 00 EF 128-130 o 33.8 2 4-di-OH 3 -thien-3-yl -G 2 CH 2 oc 215F37- 380 33.9 -CH 2 03 7-n F 43-450

33.10 "CF 3 F 94 970

  33 11 2, 4-diC H -thien-3-yl -CH O 011 F 48-490

2 3

EXAMPLE 34

  (N-4-methoxy-2-methyl-thien-3-yl) debenzyl carbamate 63.6 g are added in one go while stirring.

  (0.23 moles) of diphenylphosphorylazide and 24.4 g (0.23 moles)

  ethylamine to the suspension of 36.5 g (0.21 mole) of 4-methoxy-

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

  The mixture is refluxed for 1 hour, then

  treated with 25 g (0.23 mol) of benzyl alcohol.

  After 3.5 hours of reaction at 78, the mixture is cooled to

  The mixture is diluted with 350 ml of ethyl ether and washed successively with 250 ml of 5% HCl, 250 ml of saturated Na RCO 3 solution and 200 ml of saturated brine. The crystallized residue obtained on evaporation at room temperature. the rotary evaporator of the solvent dried over Na 2 O 4 is triturated with pentane; we obtain the desired compound of

  analytical purity melting at 107-108.

EXAMPLE 35

  Following the procedure of Example 34, with

  the appropriate carboxylic acid was obtained carbamates

  after. EXAMPLE 35 Melting benzyl 1 (N-2: 4-di-CH-furan-3-yl) carbamate

at 103-105.

  EXAMPLE 35 Benzyl 2 (N-4-n-butoxy-2-methyl-3-yl) carbamate

melting at 83.

EXAMPLE 36

  4-methoxy-2-methylthioehene-3-carboxylic acid This compound was obtained by saponification (KOH) of

  the corresponding ethyl ether; he melts at 127.

FXEMPLE 37

  By a procedure analogous to that of Example 36, 4-n-butoxy-2-methyl-thiophene-3-carboxylic acid was obtained.

melting at 66-68.

EXAMPLE 38

  4-methox-2-methylthiohebne-3-carboxylated

__ __ _ __ __ _ __ __ __ _ __

  20 ml of hydroxide solution are added dropwise

  of 50% sodium to a mixture of 18.6 g (0.1 mol) of 4-hydroxy-2-

  methyl-thiophene-3-carboxylic acid ethyl ester, 10 ml (0.105 mole) of

  dimethyl ether and 2.3 g (0.01 mole) of benzyltriethyl chloride

  ammonium in 100 ml of CH 2 Cl 2 at room temperature.

  After about 15 minutes of boiling under reflux, the desired compound is isolated from the reaction mixture; Rf = 0.36 (ether

ethyl / hexane, 2: 1).

EXAMPLE 39

  Methyl 5-dimethyl-4-nitrothiophene-2-carboxilate.

  To a solution cooled to 0 ° C. with 51: 4 g (0.3 mole) of 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 ml of acetic anhydride After the end of the addition, the brown solution is added again for 2 hours to 5 and then

poured into 3 liters of ice water.

  The aqueous phase is extracted twice with 500 ml of ethyl ether. The ether extracts are washed with water and then with 3% sodium bicarbonate solution and dried over Na 2 O 4.

evaporate under vacuum.

  The residue is subjected to chromatography on a column of silica gel. Elution with hexane / ethyl ether mixture

  : 1 gives the desired compound melting at 87-88.

EXAMPLE 40

  By a procedure analogous to that of Example 39,

  but starting from 1,3-dimethyl-1-5-ethoxypyrazole, 1,3

  dimethyl-5-ethoxy-4-nitropyrazole; Rf = 0.37 with ethyl ether / silica gel, Herbicide activity tests

EXAMPLE 41

  Weed control Pre-emergent treatment Sowing pots (7 cm diameter) are filled with a mixture of peat and sand culture substrate on the exposed surface of the culture substrate mixture. and sand,

  a liquid containing a compound according to the invention is sprayed

  for example, as described in Example B), seeds of Lepidium sativum, Agrostis alba, Avena sativa and Lolium perenne are sown in each pot; the seeds of Avena sativa and Lolium perenne, after sowing, are covered with a thin layer

  (0.5 cm) of the mixture of culture substrate / sand The pots are now

  held for 21 days at room temperature during illumination

  (daylight or equivalent) from 14 to 17 h per day.

  The determination of the herbicidal effect of the particular active compound is made after the 21-day period. This determination includes a visual assessment of the degree and

  the quality of the damage inflicted on the various sown plants.

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

act -ve per hectare.

  There is a herbicidal activity, i.e.

  significant damage to the plants under test.

EXAMPLE 42

  Action on weeds post-emergence treatment A procedure analogous to that of Example 41 is followed except that the compounds tested (herbicides) are applied while the plants are in the 2-4 leaf stage,

  the seeds sown so that the plants

  Rates reach stage 2 to 4 leaves at about the same time.

  Again, the compounds of formula I are applied as described above at doses corresponding to 1.4 kg / ha and 6 kg / ha. The determination of the herbicidal effect is made 21 days after the application of the compounds and consists of In an analogous assessment to that described in Example 41, a herbicidal activity is observed.

EXAMPLE 43

  Representative compounds of the invention are subjected to tests by the procedure described below (application

pre-emergence).

  30x40 cm sowing trays are packed at one

  6 cm filler of a mixture of peat and sand culture substrate On the exposed surface of the mixture of culture substrate and sand, a liquid spray is applied

  aqueous solution (formulated, for example, as described in Example B),

  a compound according to the invention at a given concentration.

  The spray volume corresponds to 600 liters of aqueous liquid 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 rates. In each vat, six seed species are then sown. The number of seeds

  sown for each plant species depends on the potential for germination

  seed nation and also the initial growth size of the particular plant planted After sowing, the treated surface is covered with a thin layer about 0.5 cm thick of the culture substrate mixture. peat and

sand.

  The seedbeds are then maintained for 2 to 20 days at a temperature of 20 to 24 ° C with illumination during

14 to 17 hours a day.

  Determination of the herbicidal effect of the compound

  the invention is made 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 among others with the compounds 25, 26, 47, 48, 55, 75, 84 and 86 of Table A. Some of the results obtained at an application rate corresponding to 1 kg of active ingredient per hectare

  are reported in Table B below.

EXAMPLE 44

Treatment depost-lift-

  Representative compounds of formula I are subjected to

  other tests according to a procedure of application in post-

  similar to the pre-emergence test described in

  example 43, the only difference being that the herbal liquid

  bicide is applied when the plants have reached the 2 to 4 leaf stage For this purpose, the various plant species are sown at times staggered over time The conditions prevailing in the greenhouse (temperature, light) are the same as in the example 43 Determination of the herbicidal effect is also made 28 days later

  application by the procedure of Example 41.

  Particularly advantageous herbicidal properties are observed, inter alia, with compounds Nos. 25, 26, 47, 48, 55, 75, 84 and 86 of Table A. Some of the results obtained at application rates corresponding to 5 kg of active ingredient per hectare.

  are reported in Table C below.

  TABLE B Application at pre-emergence, 1 kg / ha Mouse Compound at Damage Testing 1 Treated Plant -T- 26 71 48 55 75 -ti, 116 Amaran Retrofle No. 9 o I c'a, 100 100 100 80 go Capsella bp 80 ICO 80 90 70 7 O 91 CI Chenop alb 80 8 L) O 50 20 50 60 60 Galium aparine 80 10 50 u O 50 10, Senecio vulg 90 80 80 80 80 100 90 1 C -D Stellaria media -70 7 80 50 50 70 90 alfalfa 080 60 60 5 N 80 0 70 90 bean OO 20 20 OO 10 10 carrot 80 90 90 90 -70 8 c, 10-0 cotton 20 O 10 000 20 Olin 80 60 50 2, 0 O 201 1,1 potato O 10 10,000 soybean 30 30 O 10 30 3 C) sugar beet 10 1 COOO 2 C rapeseed 10 O 20 OOO 2 (D 10 O sunflower 1 i) j 30 50 OOO 10 Agropyron repens 90 100 90 u 90 90 70 Agrostis alba 00 11) 0 lion, 1 oral 10-0 10, y 7 o 100 Alepec myos 9O 90 80 20 50 80 80 (110 Apera sp venti 111111 1 OID 100

____ _ 1-00 1, 1 "D C,

  Z 5 Avena fatua 8 O 80 40 O 90 50 Echinochloa c g 100 -910 90 Cri 9 o 90

T S 30

  ma 20 r D 3 o C) 50 90 wheat 70 100 91 90 O 1 c O 60 10 TABLE C Post-emergence application, 7 5 kg / ha 4 Compounds tested -% damage Plant treated -2-6 __ 8 55 * 75 84 t 6 * Azxaran retroflj O oo i O, 60 80 g Capsella bp O 601 20 2? O 80 50 80 j 601 Ceo alb 90 t 4 0140 20120 40 301 601 Galiumaparin _______ 4030___ 20 ______ Senecio vulg 80 50 70 80 f 90 90 80 90 Stllri _mdi 501 60 I 10 130 t O 60) 40 alfalfa 1801 601 201 101 50 20170 7 beans 1100 2 12030 1201 20 30 j 30 I carrot 70 30 d 100 80 100 100 80 cotton lc O ) 50 J 70 l lin__ _ _ _ _ 070 90 i OV, O 90 4 80) pometer 7 O 2 1 10 I 10 1 4 I soija 90 j 3301 30 30 20 i 2 LO 501 safe beterave 302 70 VYVY 10 O rape 40 20 O 10 30 WEO 50 OJ sunflower __ 5 30 8 O 65 Agrpyonrepens 70) 30 d 70 ____ 50 SO 30 5 Alopecmyos 8 90 80 70 60 go so * 80 Apera sp eni 90 oo) oa hc 7 10 10 Avena fatua 90 100 90 80 90 100) 1oo 10 CE Finochloa cgi OO 8- 90 7

2) O 8 80 90 O

  maize (80 D 6 100 90 10 O 7 't 801 wheat 790180 50 10 10 60180 ri_ 2 _'_ 3 Io E oj 30 3 O * 4 kg / ha I) conditions on land; 2) paddy conditions M 2 <ii 2 j Field test Compound 25 was further subjected to a real test, in pre-emergence application, on multiple crops (Multicrop-Fieldscreening) under the following conditions: Soybeans ("Steele") (So) Cotton ("Stoneville 213") (Cot)

But (LG 11) (Co) -

  Wheat (Svenno) (Wh) Weeds Alopecurus-pratensis (A 1) Echinochloa crus galli (Ech) Galium aparine Chenopodium album and polyspermum dicotyledons Amaranthus retroflexus (All weeds except Alopecurus pratensis

  which has been sown, grow naturally).

  Spray volume: 750 1 / ha Number of repeated applications: 3 Appreciation: 28 days after application

  Comparative Controls: Alachlor (= α-chloro-2 ', 6'-diethyl-N-methoxy)

  methylacetanilide) and Metolachlor

  1-chloro-2'-ethyl-6'-methyl-N- (1-methyl)

  2-methoxyethyl) acétanilidel. The following herbicidal activity was observed: Compound kg / ha n 25 0.6 1.25 2.5 Alachlor 1.25

2.5

Metolachlor 1.25 2.5 So Cot

O O

3 3

7

O O

0 3

O O

0 O

Co Wh Al / Ech

Dicoty-

  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 monocotyledonous weeds.

  comparative products on dicotyledonous weeds.

  The herbicidal activity is selective for soybean, cotton and, at the lowest application rate, for corn as well.

RE VE N D ICA T ION

  3-aminothiophenes substituted in 2-positions

and 4 with C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy groups.