EP0000852B1 - Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation - Google Patents

Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation Download PDF

Info

Publication number
EP0000852B1
EP0000852B1 EP78400063A EP78400063A EP0000852B1 EP 0000852 B1 EP0000852 B1 EP 0000852B1 EP 78400063 A EP78400063 A EP 78400063A EP 78400063 A EP78400063 A EP 78400063A EP 0000852 B1 EP0000852 B1 EP 0000852B1
Authority
EP
European Patent Office
Prior art keywords
formula
ethyl
chlorine
group
dichloroacetamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78400063A
Other languages
German (de)
French (fr)
Other versions
EP0000852A1 (en
Inventor
Bernard Simon Jean-Marie Gorny
Jean-Paul Marie René Brun
Gérard Emile Marcel Boutemy
Michel Louis Devif
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Produits Chimiques Ugine Kuhlmann
Original Assignee
Produits Chimiques Ugine Kuhlmann
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Produits Chimiques Ugine Kuhlmann filed Critical Produits Chimiques Ugine Kuhlmann
Publication of EP0000852A1 publication Critical patent/EP0000852A1/en
Application granted granted Critical
Publication of EP0000852B1 publication Critical patent/EP0000852B1/en
Expired legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions

Definitions

  • the subject of the present invention is a process for treating crops to protect them from damage caused by herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and thiolcarbamates, a process which uses derivatives of dichloroacetamide or trichloroacetamide.
  • the subject of the invention is also new derivatives of dichloroacetamide or trichloroacetamide which can be used in said process, and their preparation processes.
  • herbicide antidote products which have the property of giving herbicides increased selectivity or new selectivities, without harming their herbicidal quality.
  • the antidote makes disappear completely or at least in large part, the phytotoxicity of the herbicide with respect to the cultivated plant without reducing its phytotoxicity with regard to undesirable plants.
  • R 1 is a low haloalkyl group and R is an alkyl, alkenyl, phenyl, phenalkenyl, naphthyl, cyanoalkyl or phenyl group substituted by OCH 3 , NO 2 , CI, Br, 3,4-methylenedioxy or low alkyl mono- or disrupted.
  • the method of treating crops according to the invention consists in applying to the cultivated surface, pre-emergence or post-emergence of the crop, before or after application of the herbicide or at the same time as the latter, or on the seed of cultivation an herbicide antidote compound corresponding to the formula: in which R 1 represents a dichloromethyl or trichloromethyl group, X 1 represents a chlorine or fluorine atom, X 2 represents a chlorine or fluorine atom, X 3 represents a hydrogen, chlorine or fluorine atom, R 2 represents an amino group NH 2 or a group where R 3 represents a hydrogen atom or an alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl or aryl group, the latter optionally being substituted by one or two halogen atoms or by
  • the alkyl and alkoxy chains of the alkyl, haloalkyl, arylalkyl, arylhaloalkyl, alkoxyalkyl and haloalkoxyalkyl groups preferably have 1 to 5 carbon atoms
  • the alkenyl chains of the alkenyl and haloalkenyl groups preferably 2 to 5 carbon atoms
  • the cycloalkyl and halocycloalkyl groups preferably have 3 to 6 carbon atoms
  • the haloalkyl, haloalkenyl, arylhaloalkyl, halocycloalkyl, haloalkoxyalkyl groups preferably have 1 to 7 halogen atoms taken from the chlorine atoms, bromine or fluorine
  • aryl preferably denotes phenyl and the halogen substituent of the aryl group is preferably a chlorine atom.
  • R 2 is preferably NH 2 or a group wherein R ' 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms and 1 to 7 atoms 'halogen, or a phenyl group substituted by one or two chlorine atoms.
  • R ' 3 is a haloalkyl group, it is preferably a group wherein Y 1 is a chlorine or fluorine atom, Y 2 is a chlorine or fluorine atom and Y 3 is a hydrogen, chlorine or fluorine atom.
  • the reactions (1), (2), (3), (4) are preferably carried out in an inert solvent such as for example a linear or cyclic ether, an aliphatic or aromatic hydrocarbon or a chlorinated derivative of an aliphatic or aromatic hydrocarbon , at a temperature between -30 ° C and + 60 ° C and preferably between -15 ° C and + 30 ° C.
  • the hydrochloric acid formed in the reaction is neutralized, as it is formed, by a mineral base such as for example an alkali or alkaline earth metal hydroxide or by a tertiary amine such as for example triethylamine or pyridine.
  • the product of formula (I) formed is isolated in the crude state by elimination of the solvent by distillation. It can be purified, for example by recrystallization, or used as it is.
  • the compounds of formula (1) for which R 2 is an NH 2 group, which are identical to the compounds of formula (II), and the compounds of formula (III) can be prepared by the action of ammonia on the chlorinated derivatives of formulas (IV) and (V).
  • the reaction is carried out in the same solvents as those used for reactions (1) to (4) and preferably in a cyclic ether such as for example tetrahydrofuran.
  • the chlorinated derivative of formula (IV) or (V) is introduced into the solvent saturated with ammonia, at a temperature between - 30 ° C and + 30 ° C.
  • the ammonium chloride formed is eliminated by filtration and the compound of formula (II) or (III) is isolated in the crude state by elimination of the solvent. It can be purified by recrystallization or used as such, in particular for carrying out reactions (1) or (2).
  • the compounds of formula (IV) and (V) can be prepared by the action of thionyl chloride on the hydroxylated compounds of formulas: in which R 1 , R 3 , X 1 , X 2 , X 3 have the same meanings as in formula (I).
  • the reaction can be carried out, in the presence or not of a solvent, with an excess of thionyl chloride, at a temperature between 50 ° C. and 80 ° C.
  • the solvent used can be identical to those used to carry out reactions (1) to (4). In the case where one operates without solvent, and also when one operates with certain solvents such as for example CCI 4 or hexane, the compound of formula (IV) or (V) precipitates and can be isolated by filtration.
  • the compound of formula (IV) or (V) does not precipitate.
  • the hydroxylated compounds of formulas (VI) or (VII) can be prepared by the action of an amide of formula on a halogenated aldehyde of formula following the procedures described by Joseph P. LAROCCA, John M. LEONARD, Warren E. WEAVER [Journal of Organic Chemistry 16, 47-50, (1951)] and by A. BOUCHERLE, G. CARRAZ, J. VIGIER [Bull. Trav. Soc. Pharm. Lyon 10 (1), 3-10, (1966)].
  • the compounds of formula (I) can be used, as herbicide antidotes, for the treatment of crops. They protect cultivated plants against damage caused by herbicides, and this at doses of herbicides effective against undesirable plants.
  • the compounds of formula (I) can in particular be used in combination with herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates.
  • herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates.
  • EPTC ethyl N, N-dipropyl thiolcarbamate
  • butylate butylate
  • N N-dipropyl thiolcarbamate
  • N- ethyl diethyl thiolcarbamate etholate
  • ethyl N-ethyl N-cyclohexyl thiolcarbamate cycloate
  • the compounds of formula (I) can be incorporated, jointly with the herbicide or separately, in compositions which contain, in addition to the active material (that is to say the antidote compound and optionally the herbicide ), the inert additives usually used in agriculture to facilitate the conservation, the implementation and the penetration into plants of the active products, such as mineral fillers (talc, silica, kieselguhr, diatomaceous earth, clay etc.), organic diluents various (mineral oils, organic solvents), surfactants, antioxidants and stabilizers.
  • Such compositions can be in the form of wettable powders, solutions emulsifiable in water, granules or any other form used in the field of herbicides.
  • the content of antidote compound can vary from 10% to 90% by weight.
  • the content of antidote compound can vary from 0.09% to 50% by weight, that in herbicide from 1% to 90% by weight, the weight ratio
  • the antidote compounds according to the invention can be applied to the soil at the same time as the herbicide, pre-emergence or post-emergence of the crop.
  • the dose of antidote product provided can vary from 100 g to 5000 g per hectare.
  • compositions containing the antidote product and the herbicide simultaneously such as those mentioned above.
  • the antidote compounds according to the invention can also be applied to the soil at a time different from that of the treatment with the herbicide, pre-emergence or post-emergence of the crop, the dose of antidote product provided being the same as above. They can in particular be applied to soils containing herbicide residues in order to protect crops against the residual activity of these residues.
  • the antidote compounds according to the invention can also be applied to the seed of the crop to be protected, said seed then being sown in soil already treated with the herbicide or which will be treated with the herbicide.
  • the dose of antidote provided can vary from 10 g to 500 g per quintal of seed.
  • N - [(2,2-dichloro-1 amino-1) ethyl] dichloroacetamide used as starting material can be prepared as indicated in Example 14.
  • N - [(2,2,2-trichloro-1,2 amino-1) ethyl] formamide By operating as in Example 1, but replacing N - [(2,2,2-trichloro-1,2 amino-1) ethyl] formamide by N - [(2,2,2-trichloro-amino-1) ethyl] acetamide, N - [(2,2,2-trichloro-1-dichloroacetamido) ethyl] acetamide is obtained with a yield of 61.5%, melting point 239-240 ° C.
  • the N - [(2,2,2-trichloro-1 amino-1) ethyl] acetamide used as a starting product is prepared according to the method used to prepare the N - [(2,2,2-trichloro-1 amino) ethyl] trichloroacetamide, but by replacing the 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide with 320 g of N - [(tetrachloro-1,2,2,2) ethyl] acetamide (1, 42 mole). The addition to THF saturated with ammonia is carried out in 1 h 45 '.
  • Example 3 By operating in Example 3, but by replacing the dichloroacetamide and the N - [(tetrachloro-1, 2,2,2) ethyl] dichloroacetamide by respectively the formamide and the N - [(trichloro-1,2,2) ethyl] dichloroacetamide, N - [(2,2-dichloroacetamido-1) ethyl] formamide, with melting point 79-80 o C., is obtained with a yield of 74.6%.
  • a soil consisting of two parts by weight of clay and three parts by weight of sand, is spread in plastic tubs of dimensions 18 x 12 x 5 cm. On this seed we sow, in 4 furrows of 0.5 cm deep, 10 corn seeds, variety "Sandrina", and 10 barley seeds, variety "Rika.”
  • the seedlings thus produced are separated into 3 batches, each batch containing 5 trays.
  • On the 1st batch spread a layer, 2cm thick, of soil that has not undergone any treatment.
  • On the 2nd batch spread a layer, 2 cm thick, of soil in which we have incorporated by careful mixing a naturally phytotoxic herbicide for corn at the dose where it is applied.
  • the herbicide and the antidote are formulated in the form of aqueous suspensions.
  • the quantities of herbicide applied correspond to doses of herbicides of 5 kg and 10 kg / ha.
  • the amounts of antidote product provided correspond to doses equal to one tenth of the doses of the herbicide, ie 0.5 and 1 kg / ha.
  • the herbicide used is E.P.T.C. or N, N, ethyl dipropyl thiolcarbamate.
  • the antidote products tested are the compounds of Examples 1 to 15.
  • the batches of trays, once treated, are placed in a greenhouse maintained at 20 ° C and at a humidity rate of 70%. 12 and 20 days after the treatment (D + 12; D + 20), the batches are examined and the herbicidal efficacy of the “antidote + herbicidal combination” is determined on the one hand and on the other hand the antidote efficacy of the compound according to the invention tested. Antidote E efficacy is evaluated by measuring the average height of the maize plants in the three batches.
  • A denotes the average size of the corn plants in the untreated control lots
  • B the average size of the corn plants in the lots treated with the herbicide alone
  • C the average size of the corn plants in the lots treated with l herbicide and antidote.
  • Example 1 the product of Example 1 was tested according to the method described in the previous example, but by varying the dose of the antidote product relative to that of the associated herbicide (EPTC).
  • the herbicide was applied at the dose of 5 kg / ha and the product of Example 1 at the doses 0 kg / ha (tests with herbicide alone), 0.312 kg / ha, 0.625 kg / ha, 1.250 kg / ha and 2,500 kg / ha.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

La présente invention a pour objet un procédé de traitement des cultures pour les protéger contre les dommages occasionnés par les herbicides appartenant aux familles des chloroacétanilides, urées, triazines, carbamates, uraciles et thiolcarbamates, procédé qui utilise des dérivés de dichloroacétamide ou de trichloroacétamide. L'invention a également pour objet de nouveaux dérivés de dichloroacétamide ou de trichloroacétamide utilisables dans ledit procédé, et leurs procédés de préparation.The subject of the present invention is a process for treating crops to protect them from damage caused by herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and thiolcarbamates, a process which uses derivatives of dichloroacetamide or trichloroacetamide. The subject of the invention is also new derivatives of dichloroacetamide or trichloroacetamide which can be used in said process, and their preparation processes.

Les herbicides existant actuellement peuvent être classés en deux catégories: les herbicides totaux, qui détruisent toutes les plantes, et les herbicides sélectifs. Ces derniers, qui sont les plus précieux en agriculture, permettent de détruire les mauvaises herbes présentes dans les cultures sans nuire à la plante cultivée et sont dits, pour cette raison, sélectifs de la plante cultivée. Malheureusement il arrive que cette sélectivité ne soit pas parfaite à la dose d'emploi et que les herbicides sélectifs présentent une certaine phytotoxicité vis-à-vis de la plante cultivée.Currently existing herbicides can be classified into two categories: total herbicides, which destroy all plants, and selective herbicides. The latter, which are the most precious in agriculture, allow to destroy the weeds present in the crops without harming the cultivated plant and are said, for this reason, selective of the cultivated plant. Unfortunately it sometimes happens that this selectivity is not perfect at the dose of use and that the selective herbicides present a certain phytotoxicity with respect to the cultivated plant.

Aussi utilise-t-on, en association avec les herbicides, des produits dits antidotes d'herbicides qui ont la propriété de conférer aux herbicides une sélectivité accrue ou des sélectivités nouvelles, sans nuire à leur qualité herbicide. Autrement dit l'antidote fait disparaitre totalement ou tout au moins en grande partie, la phytotoxicité de l'herbicide vis-à-vis de la plante cultivée sans réduire sa phytotoxicité vis-à-vis des plantes indésirables.So we use, in combination with herbicides, so-called herbicide antidote products which have the property of giving herbicides increased selectivity or new selectivities, without harming their herbicidal quality. In other words, the antidote makes disappear completely or at least in large part, the phytotoxicity of the herbicide with respect to the cultivated plant without reducing its phytotoxicity with regard to undesirable plants.

De tels produits antidotes d'herbicides ont par exemple été décrits dans les brevets français Nos 2 133 793, 2 212 336, 2 215 170, 2 228 065, 2 309 546 et 2 310 348 et dans les brevets US Nos 3 867 444, 3 923 494, 3 931 313 et 3 959 304. Le brevet US 3 923 494 en particulier décrit des composés antidotes d'herbicides répondant à la formule:Such herbicide antidote products have for example been described in French patents Nos. 2,133,793, 2,212,336, 2,215,170, 2,228,065, 2,309,546 and 2,310,348 and in US patents Nos. 3,867,444, 3,923,494, 3,931,313 and 3,959,304. US Pat. 3,923,494 in particular describes antidote compounds of herbicides corresponding to the formula:

Figure imgb0001
dans laquelle R1 est un groupe haloalkyle bas et R est un groupe alkyle, alcényle, phényle, phénalcényle, naphtyl, cyanoalkyle ou phényl substitué par OCH3, N02, CI, Br, méthylènedioxy-3,4 ou alkyl bas mono- ou disubstitué.
Figure imgb0001
 in which R 1 is a low haloalkyl group and R is an alkyl, alkenyl, phenyl, phenalkenyl, naphthyl, cyanoalkyl or phenyl group substituted by OCH 3 , NO 2 , CI, Br, 3,4-methylenedioxy or low alkyl mono- or disrupted.

Il est en outre connu par le DE - A - 2 047 258 des N,N-trichloréthylidène-bis-amides ou - thiocarbamides de formule:

Figure imgb0002
dans laquelle R1 et R2 sont différents, R1 représente un atome d'hydrogène ou un groupe alkyle, aryle ou cycloalkyle éventuellement substitué par des atomes d'halogène ou des groupes nitro et R2 représente un groupe alkyle, aryle, cycloalkyle, alkylthio, arylthio ou cycloalkylthio éventuellement substitué par des atomes d'halogène ou des groupes nitro. Ces composés peuvent être utilisés comme produits intermédiaires ou finaux pour la préparation de médicaments ou de biocides. Il n'est pas indiqué dans le DE - A - 2 047 258 que ces composés soient utilisables comme antidotes d'herbicides.It is also known from DE - A - 2,047,258 N, N-trichlorethylidene-bis-amides or - thiocarbamides of formula:
Figure imgb0002
 in which R 1 and R 2 are different, R 1 represents a hydrogen atom or an alkyl, aryl or cycloalkyl group optionally substituted by halogen atoms or nitro groups and R 2 represents an alkyl, aryl, cycloalkyl group, alkylthio, arylthio or cycloalkylthio optionally substituted by halogen atoms or nitro groups. These compounds can be used as intermediate or final products for the preparation of drugs or biocides. DE - A - 2 047 258 does not indicate that these compounds can be used as antidotes for herbicides.

Le procédé de traitement des cultures selon l'invention consiste à appliquer sur la surface cultivée, en prélevée ou en post-levée de la culture, avant ou après application de l'herbicide ou en même temps que ce dernier, ou sur la semence de la culture un composé antidote d'herbicides répondant à la formule:

Figure imgb0003
dans laquelle R1 représente un groupement dichlorométhyle ou trichlorométhyle, X1 représente un atome de chlore ou de fluor, X2 représente un atome de chlore ou de fluor, X3 représente un atome d'hydrogène, de chlore ou de fluor, R2 représente un groupe amino NH2 ou un groupe
Figure imgb0004
 où R3 représente un atome d'hydrogène ou un groupe alkyle, haloalkyle, alkényle, haloalkényle, arylalkyle, arylhaloalkyle, cycloalkyle, halocycloalkyle, alcoxyalkyle, haloalcoxyalkyle ou aryle, ce dernier étant éventuellement substitué par un ou deux atomes d'halogène ou par un groupe alkyle, alcoxy, nitro ou haloalkyle.The method of treating crops according to the invention consists in applying to the cultivated surface, pre-emergence or post-emergence of the crop, before or after application of the herbicide or at the same time as the latter, or on the seed of cultivation an herbicide antidote compound corresponding to the formula:
Figure imgb0003
 in which R 1 represents a dichloromethyl or trichloromethyl group, X 1 represents a chlorine or fluorine atom, X 2 represents a chlorine or fluorine atom, X 3 represents a hydrogen, chlorine or fluorine atom, R 2 represents an amino group NH 2 or a group
Figure imgb0004
 where R 3 represents a hydrogen atom or an alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl or aryl group, the latter optionally being substituted by one or two halogen atoms or by a alkyl, alkoxy, nitro or haloalkyl group.

Dans les définitions données ci-dessus pour R3, les chaînes alkyle et alcoxy des groupes alkyle, haloalkyle, arylalkyle, arylhaloalkyle, alcoxyalkyle et haloalcoxyalkyle ont de préférence 1 à 5 atomes de carbone, les chaînes alkényle des groupes alkényle et haloalkényle ont de préférence 2 à 5 atomes de carbone, les groupes cycloalkyle et halocycloalkyle ont de préférence 3 à 6 atomes de carbone, les groupes haloalkyle, haloalkényle, arylhaloalkyle, halocycloalkyle, haloalcoxyalkyle ont de préférence 1 à 7 atomes d'halogène pris parmi les atomes de chlore, brome ou fluor, aryl désigne de préférence phényl et le substituant halogène du groupe aryle est de préférence un atome de chlore.In the definitions given above for R 3 , the alkyl and alkoxy chains of the alkyl, haloalkyl, arylalkyl, arylhaloalkyl, alkoxyalkyl and haloalkoxyalkyl groups preferably have 1 to 5 carbon atoms, the alkenyl chains of the alkenyl and haloalkenyl groups preferably 2 to 5 carbon atoms, the cycloalkyl and halocycloalkyl groups preferably have 3 to 6 carbon atoms, the haloalkyl, haloalkenyl, arylhaloalkyl, halocycloalkyl, haloalkoxyalkyl groups preferably have 1 to 7 halogen atoms taken from the chlorine atoms, bromine or fluorine, aryl preferably denotes phenyl and the halogen substituent of the aryl group is preferably a chlorine atom.

Dans la formule (I) ci-dessus R2 est de préférence NH2 ou un groupe

Figure imgb0005
dans lequel R'3 est un atome d'hydrogène, un groupe alkyle ayant 1 à 5 atomes de carbone, un groupe alcényle ayant 2 à 5 atomes de carbone, un groupe haloalkyle ayant 1 à 5 atomes de carbone et 1 à 7 atomes d'halogène, ou un groupe phényle substitué par un ou deux atomes de chlore. Quant R'3 est un groupe haloalkyle, il est de préférence un groupe
Figure imgb0006
dans lequel Y1 est un atome de chlore ou de fluor, Y2 est un atome de chlore ou de fluor et Y3 est un atome d'hydrogène, de chlore ou de fluor.In formula (I) above R 2 is preferably NH 2 or a group
Figure imgb0005
 wherein R ' 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms and 1 to 7 atoms 'halogen, or a phenyl group substituted by one or two chlorine atoms. When R ' 3 is a haloalkyl group, it is preferably a group
Figure imgb0006
 wherein Y 1 is a chlorine or fluorine atom, Y 2 is a chlorine or fluorine atom and Y 3 is a hydrogen, chlorine or fluorine atom.

Les composés de formule (I) pour lesquels R2 représente un groupe amino NH2 sont des produits nouveaux. De même les composés de formule (I) pour lesquels X1, X2, X3 ne sont pas tous les trois des atomes de chlore et R2 est un groupe

Figure imgb0007

  • R3 ayant les significations indiquées à la formule (I), sont des produits nouveaux.
The compounds of formula (I) for which R 2 represents an amino group NH 2 are new products. Similarly, the compounds of formula (I) for which X 1 , X 2 , X 3 are not all three chlorine atoms and R 2 is a group
Figure imgb0007
  • R 3 having the meanings indicated in formula (I), are new products.

Les composés de formule (I) pour lesquels R2 est un groupe

Figure imgb0008
en particulier ceux qui sont nouveaux, peuvent être préparés par plusieurs méthodes, à savoir:

  • 1 °) action d'un chlorure d'acide de formule
    Figure imgb0009
    sur un composé aminé de formule (II) ci-dessous suivant la réaction:
    Figure imgb0010
  • 2°) action d'un chlorure d'acide de formule
    Figure imgb0011
     sur un composé aminé de formule (III) ci-dessous suivant la réaction:
    Figure imgb0012
  • 3°) action d'un amide de formule
    Figure imgb0013
    sur un dérivé chloré de formule (IV) ci-dessous suivant la réaction:
    Figure imgb0014
  • 4°) action d'un amide de formule
    Figure imgb0015
    sur un dérivé chloré de formule (V) ci-dessous suivant la réaction:
    Figure imgb0016
The compounds of formula (I) for which R 2 is a group
Figure imgb0008
 in particular those which are new, can be prepared by several methods, namely:
  • 1) action of an acid chloride of formula
    Figure imgb0009
     on an amino compound of formula (II) below depending on the reaction:
    Figure imgb0010
  • 2) action of an acid chloride of formula
    Figure imgb0011
     on an amino compound of formula (III) below depending on the reaction:
    Figure imgb0012
  • 3) action of an amide of formula
    Figure imgb0013
     on a chlorinated derivative of formula (IV) below depending on the reaction:
    Figure imgb0014
  • 4) action of an amide of formula
    Figure imgb0015
     on a chlorinated derivative of formula (V) below depending on the reaction:
    Figure imgb0016

Dans les formules (II), (III), (IV), (V) ci-dessus ainsi que dans celles des chlorures d'acide et amides, X1, X2, X3, R1 et R3 ont les mêmes significations que dans la formule (I).In formulas (II), (III), (IV), (V) above as well as in those of acid chlorides and amides, X 1 , X 2 , X 3 , R 1 and R 3 have the same meanings as in formula (I).

Les réactions (1), (2), (3), (4) sont effectuées de préférence dans un solvant inerte tel par exemple un éther linéaire ou cyclique, un hydrocarbure aliphatique ou aromatique ou un dérivé chloré d'un hydrocarbure aliphatique ou aromatique, à une température comprise entre -30°C et +60°C et de préférence entre -15°C et +30°C. L'acide chlorhydrique formé dans la réaction est neutralisé, au fur et à mesure de sa formation, par une base minérale comme par exemple un hydroxyde de métal alcalin ou alcalino-terreux ou par une amine tertiaire comme par exemple la triéthylamine ou la pyridine. Après séparation par extraction à l'eau ou par filtration du chlorure de la base minérale ou du chlorhydrate de l'amine, le produit de formule (I) formé est isolé à l'état brut par élimination du solvant par distillation. Il peut être purifié, par exemple par recristallisation, ou utilisé tel quel.The reactions (1), (2), (3), (4) are preferably carried out in an inert solvent such as for example a linear or cyclic ether, an aliphatic or aromatic hydrocarbon or a chlorinated derivative of an aliphatic or aromatic hydrocarbon , at a temperature between -30 ° C and + 60 ° C and preferably between -15 ° C and + 30 ° C. The hydrochloric acid formed in the reaction is neutralized, as it is formed, by a mineral base such as for example an alkali or alkaline earth metal hydroxide or by a tertiary amine such as for example triethylamine or pyridine. After separation by extraction with water or by filtration of the chloride of the mineral base or of the hydrochloride of the amine, the product of formula (I) formed is isolated in the crude state by elimination of the solvent by distillation. It can be purified, for example by recrystallization, or used as it is.

Les composés de formule (1) pour lesquels R2 est un groupe NH2, qui sont identiques aux composés de formule (II), et les composés de formule (III) peuvent être préparés par action de l'ammoniac sur les dérivés chlorés de formules (IV) et (V). La réaction est réalisée dans les mêmes solvants que ceux utilisés pour les réactions (1) à (4) et de préférence dans un éther cyclique comme par exemple le tétrahydrofuranne. Le dérivé chloré de formule (IV) ou (V) est introduit dans le solvant saturé en ammoniac, à une température comprise entre - 30°C et + 30°C. Le chlorure d'ammonium formé est éliminé par filtration et le composé de formule (II) ou (III) est isolé à l'état brut par élimination du solvant. Il peut être purifié par recristallisation ou utilisé tel quel, en particulier pour effectuer les réactions (1) ou (2).The compounds of formula (1) for which R 2 is an NH 2 group, which are identical to the compounds of formula (II), and the compounds of formula (III) can be prepared by the action of ammonia on the chlorinated derivatives of formulas (IV) and (V). The reaction is carried out in the same solvents as those used for reactions (1) to (4) and preferably in a cyclic ether such as for example tetrahydrofuran. The chlorinated derivative of formula (IV) or (V) is introduced into the solvent saturated with ammonia, at a temperature between - 30 ° C and + 30 ° C. The ammonium chloride formed is eliminated by filtration and the compound of formula (II) or (III) is isolated in the crude state by elimination of the solvent. It can be purified by recrystallization or used as such, in particular for carrying out reactions (1) or (2).

Les composés de formule (IV) et (V) peuvent être préparés par action du chlorure de thionyle sur les composés hydroxylés de formules:

Figure imgb0017
dans lesquelles R1, R3, X1, X2, X3 ont les mêmes significations que dans la formule (I). La réaction peut être réalisée, en présence ou non d'un solvant, avec un excès de chlorure de thionyle, à une température comprise entre 50°C et 80°C. Le solvant utilisé peut être identique à ceux utilisés pour effectuer les réactions (1) à (4). Dans le cas où on opère sans solvant, et aussi quand on opère avec certains solvants comme par exemple CCI4 ou l'hexane, le composé de formule (IV) ou (V) précipite et peut être isolé par filtration.The compounds of formula (IV) and (V) can be prepared by the action of thionyl chloride on the hydroxylated compounds of formulas:
Figure imgb0017
 in which R 1 , R 3 , X 1 , X 2 , X 3 have the same meanings as in formula (I). The reaction can be carried out, in the presence or not of a solvent, with an excess of thionyl chloride, at a temperature between 50 ° C. and 80 ° C. The solvent used can be identical to those used to carry out reactions (1) to (4). In the case where one operates without solvent, and also when one operates with certain solvents such as for example CCI 4 or hexane, the compound of formula (IV) or (V) precipitates and can be isolated by filtration.

Dans le cas où on opère avec d'autres solvants comme par exemple le tétrahydrofuranne, le composé de formule (IV) ou (V) ne précipite pas. On peut alors soit isoler le produit en évaporant sous vide le solvant, soit utiliser directement le milieu obtenu en fin de réaction pour la suite du processus conduisant aux composés (I), sans isoler les produits (IV) ou (V).In the case where one operates with other solvents such as for example tetrahydrofuran, the compound of formula (IV) or (V) does not precipitate. One can then either isolate the product by evaporating the solvent under vacuum, or use the medium obtained at the end of the reaction directly for the rest of the process leading to the compounds (I), without isolating the products (IV) or (V).

Les composés hydroxylés de formules (VI) ou (VII) peuvent être préparés par action d'un amide de formule

Figure imgb0018
sur un aldéhyde halogéné de formule
Figure imgb0019
suivant les procédés décrits par Joseph P. LAROCCA, John M. LEONARD, Warren E. WEAVER [Journal of Organic Chemistry 16, 47-50, (1951)] et par A. BOUCHERLE, G. CARRAZ, J. VIGIER [Bull. Trav. Soc. Pharm. Lyon 10 (1), 3-10, (1966)].The hydroxylated compounds of formulas (VI) or (VII) can be prepared by the action of an amide of formula
Figure imgb0018
 on a halogenated aldehyde of formula
Figure imgb0019
 following the procedures described by Joseph P. LAROCCA, John M. LEONARD, Warren E. WEAVER [Journal of Organic Chemistry 16, 47-50, (1951)] and by A. BOUCHERLE, G. CARRAZ, J. VIGIER [Bull. Trav. Soc. Pharm. Lyon 10 (1), 3-10, (1966)].

Les composés de formule (I) peuvent être utilisés, en tant qu'antidotes d'herbicides, pour le traitement des cultures. Ils protègent les plantes cultivées contre les dommages occasionnés par les herbicides, et ce aux doses d'herbicides efficaces vis-à-vis des plantes indésirables.The compounds of formula (I) can be used, as herbicide antidotes, for the treatment of crops. They protect cultivated plants against damage caused by herbicides, and this at doses of herbicides effective against undesirable plants.

Les composés de formule (I) peuvent en particulier être employés en association avec les herbicides appartenant aux familles des chloroacétanilides, urées, triazines, carbamates, uraciles et plus spécialement des thiolcarbamates. Comme tels on peut citer par exemple le N,N-dipropyl thiolcarbamate d'éthyle (EPTC), le N,N-diisobutyl thiolcarbamate d'éthyle (butylate), le N,N-dipropyl thiolcarbamate de propyle, le N,N-diéthyl thiolcarbamate d'éthyle (éthiolate), le N,N-cyclohexaméthylène thiolcarbamate d'éthyle (molinate), le N-éthyl N-cyclohexyl thiolcarbamate d'éthyle (cycloate), le N,N-diisopropyl thiolcarbamate de dichloro-2,3 propényle (diallate), le N,N-diisopropyl thiolcarbamate d'éthyle, le N-(chloro-3 phényl) carbamate de chloro-4 butynyle-2 (barban), la (chloro-3 méthyl-4 phényl)-3 diméthyl-1, urée (chlortoluron), la (dichloro-3,4 phényl)-3 méthoxy-1 méthyl-1 urée (linuron), la (dichloro-3,4 phényl)-3 diméthyi-1,1 urée, la N-chloroacétyl N-isopropyl aniline (propachlor), la diéthyl-2,6 N-chloroacétyl N-méthoxyméthyl aniline (alachlor), la chloro-2 éthylamino-4 isopropylamino-6 triazine-1,3,5 (atrazine), la chloro-2 bis (éthylamino)-4,6 triazine-1,3,5 la chloro-2 cyclopropylamino-4 isopropylamino-6 triazine-1,3,5 et leurs combinaisons. Le rapport en poids produit antidoteThe compounds of formula (I) can in particular be used in combination with herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates. As such, mention may be made, for example, of ethyl N, N-dipropyl thiolcarbamate (EPTC), of ethyl N, N-diisobutyl thiolcarbamate (butylate), of N, N-dipropyl thiolcarbamate, of N, N- ethyl diethyl thiolcarbamate (etholate), ethyl N, N-cyclohexamethylene thiolcarbamate (molinate), ethyl N-ethyl N-cyclohexyl thiolcarbamate (cycloate), dichloro-2 N, N-diisopropyl thiolcarbamate, 3 propenyl (diallate), N, N-diisopropyl thiolcarbamate, N- (3-chloro-phenyl) carbamate-4-chloro-2-butynyl (barban), (3-chloro-4-methylphenyl) 1-dimethyl, urea (chlortoluron), (3,4-dichloro-phenyl) -3 1-methoxy-1-methyl-urea (linuron), (3,4-dichloro-phenyl) -3 dimethyl-1,1 urea N-chloroacetyl N-isopropyl aniline (propachlor), 2,6-diethyl N-chloroacetyl N-methoxymethyl aniline (alachlor), 2-chloro-4-ethylamino-isopropylamino-6 triazine-1,3,5 (atrazine) 2-chloro bis (ethylamino) -4,6 triazine-1,3,5 2-chloro cyclopropylamino-4 isopropylamino-6 triazi ne-1,3,5 and combinations thereof. The antidote product weight ratio

herbicideherbicide à employer peut varier beaucoup selon la nature de l'herbicide concerné. Ce rapport est en général compris entre 0,001 et 10, et le plus souvent entre 0,01 et 5.use may vary greatly depending on the nature of the herbicide involved. This ratio is generally between 0.001 and 10, and most often between 0.01 and 5.

Pour leur mise en oeuvre les composés de formule (I) peuvent être incorporés, conjointement avec l'herbicide ou séparément, dans des compositions que contiennent, outre la matière active (c'est-à-dire le composé antidote et éventuellement l'herbicide), les additifs inertes habituellement utilisés en agriculture pour faciliter la conservation, la mise en oeuvre et la pénétration dans les plantes des produits actifs, tels que charges minérales (talc, silice, kieselguhr, terre de diatomées, argile etc.), diluants organiques divers (huiles minérales, solvants organiques), tensioactifs, antioxydants et stabilisants. De telles compositions peuvent se présente sous la forme de poudres mouillables, solutions émulsifiables dans l'eau, granulés ou toute autre forme en usage dans le domaine des herbicides. Dans les compositions contenant seulement un composé antidote selon l'invention et des additifs inertes, le teneur en composé antidote peut varier de 10% à 90% en poids. Dans les compositions contenant un composé antidote selon l'invention, un herbicide et des additifs inertes, la teneur en composé antidote peut varier de 0,09% à 50% en poids, celle en herbicide de 1 % à 90% en poids, le rapport en poidsFor their use, the compounds of formula (I) can be incorporated, jointly with the herbicide or separately, in compositions which contain, in addition to the active material (that is to say the antidote compound and optionally the herbicide ), the inert additives usually used in agriculture to facilitate the conservation, the implementation and the penetration into plants of the active products, such as mineral fillers (talc, silica, kieselguhr, diatomaceous earth, clay etc.), organic diluents various (mineral oils, organic solvents), surfactants, antioxidants and stabilizers. Such compositions can be in the form of wettable powders, solutions emulsifiable in water, granules or any other form used in the field of herbicides. In the compositions containing only an antidote compound according to the invention and inert additives, the content of antidote compound can vary from 10% to 90% by weight. In the compositions containing an antidote compound according to the invention, a herbicide and inert additives, the content of antidote compound can vary from 0.09% to 50% by weight, that in herbicide from 1% to 90% by weight, the weight ratio

produits antidoteantidote products herbicideherbicide étant compris entre 0,001 et 10.being between 0.001 and 10.

Les composés antidotes selon l'invention peuvent être appliqués sur le sol en même temps que l'herbicide, en prélevée ou en post-levée de la culture. La dose en produit antidote apportée peut varier de 100 g à 5000 g par hectare. Pour une telle application il est avantageux d'utiliser des compositions contenant simultanément le produit antidote et l'herbicide, telles que celles citées précédemment.The antidote compounds according to the invention can be applied to the soil at the same time as the herbicide, pre-emergence or post-emergence of the crop. The dose of antidote product provided can vary from 100 g to 5000 g per hectare. For such an application, it is advantageous to use compositions containing the antidote product and the herbicide simultaneously, such as those mentioned above.

Les composés antidotes selon l'invention peuvent aussi être appliqués sur le sol à une époque différente de celle du traitement par l'herbicide, en pré-levée ou en post-levée de la culture, la dose en produit antidote apportée étant la même que ci-dessus. Ils peuvent en particulier être appliqués sur des sols contenant des résidus d'herbicide afin de protéger les cultures contre l'activité rémanente de ces résidus.The antidote compounds according to the invention can also be applied to the soil at a time different from that of the treatment with the herbicide, pre-emergence or post-emergence of the crop, the dose of antidote product provided being the same as above. They can in particular be applied to soils containing herbicide residues in order to protect crops against the residual activity of these residues.

Enfin les composés antidotes selon l'invention peuvent aussi être appliqués sur la semence de la culture à protéger, ladite semence étant ensuite semée dans une terre déjà traitée avec l'herbicide ou qui sera traitée avec l'herbicide. Pour le traitement des semences la dose en produit antidote apportée peut varier de 10 g à 500 g par quintal de semence.Finally, the antidote compounds according to the invention can also be applied to the seed of the crop to be protected, said seed then being sown in soil already treated with the herbicide or which will be treated with the herbicide. For the treatment of seeds, the dose of antidote provided can vary from 10 g to 500 g per quintal of seed.

Les exemples suivants illustrent l'invention sans la limiter.The following examples illustrate the invention without limiting it.

EXEMPLE N° 1EXAMPLE 1 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0020
Figure imgb0020

On dissout 19,15 g (0,1 mole) de N-[(trichloro-2,2,2 amino-1) éthyl] formamide dans 200 ml de tétrahydrofuranne (THF). On ajoute 10,1 g de triéthylamine (0,1 mole). En maintenant la température à 15°C, on ajoute sous agitation, en environ 30 minutes, 14,75 g de chlorure de dichloroacétyle (0,1 mole) dissous dans 100 ml de THF. On maintient ensuite 1/2 heure sous agitation en laissant revenir à la température ambiante. On filtre le précipité de chlorhydrate de triéthylamine. On élimine le THF par distillation sous vide. Au cours de la distillation, il se forme un produit cristallisé qui est séparé. Ce produit est recristallisé dans un mélange benzène-hexane 50-50. On obtient ainsi 24,5 g (soit un rendement de 81%) de N-[(trichloro-2,2,2 dichloroacétamido-1 ) éthyl] formamide, de point de fusion 141-142°C.19.15 g (0.1 mol) of N - [(2,2,2-trichloro-1 amino-1) ethyl] formamide are dissolved in 200 ml of tetrahydrofuran (THF). 10.1 g of triethylamine (0.1 mole) are added. Maintaining the temperature at 15 ° C., 14.75 g of dichloroacetyl chloride (0.1 mol) dissolved in 100 ml of THF are added with stirring over approximately 30 minutes. Then maintained for 1/2 hour with stirring, allowing to return to room temperature. The precipitate of triethylamine hydrochloride is filtered. THF is removed by vacuum distillation. During distillation, a crystallized product is formed which is separated. This product is recrystallized from a benzene-hexane mixture 50-50. 24.5 g are thus obtained (ie a yield of 81%) of N - [(2,2,2-trichloro-dichloroacetamido-1) ethyl] formamide, with a melting point of 141-142 ° C.

EXEMPLE N° 2EXAMPLE 2 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0021
Figure imgb0021

On sature 300 ml de tétrahydrofuranne par de l'ammoniac gazeux et on maintient cette saturation pendant toute la durée de l'opération. En maintenant la température à -5°C, on ajoute sous agitation, en environ 1 h 30 minutes, 150 g (0,5 mole) de N-[(tétrachloro-1,2,2,2) éthyl] dichloroacétamide. Il se forme tout au long de l'addition un précipité de chlorure d'ammonium. Celui-ci est séparé du milieu par filtration. Le THF est ensuite séparé par distillation sous vide. On obtient de cette façon 130 g de N-[(trichloro-2,2,2 amino-1) éthyl] dichloroacétamide (soit un rendement de 94,7%), sous la forme d'un solide blanc de point de fusion 132­- 133°C.300 ml of tetrahydrofuran are saturated with gaseous ammonia and this saturation is maintained throughout the duration of the operation. Maintaining the temperature at -5 ° C., 150 g (0.5 mol) of N - [(tetrachloro-1,2,2,2) ethyl] dichloroacetamide are added, with stirring, over approximately 1 hour 30 minutes. A precipitate of ammonium chloride is formed throughout the addition. This is separated from the medium by filtration. THF is then separated by vacuum distillation. This gives 130 g of N - [(2,2,2-trichloro-1 amino-1) ethyl] dichloroacetamide (a yield of 94.7%), in the form of a white solid with melting point 132 - 133 ° C.

EXEMPLE N° 3EXAMPLE NO.3 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0022
On dissout 10,2 g de dichloroacétamide (0,08 mole) dans 150 ml de chloroforme. On ajoute 10 g de triéthylamine (0,1 mole). En maintenant la température au voisinage de 0°C, on ajoute sous agitation, en environ 1 h, 23,5 g de N-[(tétrachloro-1,2,2,2) éthyl] dichloroacétamide (0,08 mole) dissous dans 150 ml de chloroforme. On laisse revenir à température ambiante sous agitation, puis on reprend par 1 litre d'eau. Après décantation, la phase organique est séparée et lavée deux fois avec 500 ml d'eau, puis séchée sur sulfate de magnésium. Le chloroforme est distillé sous vide et on obtient un solide qui est recristallisé dans l'hexane. On obtient ainsi 24,5 g de N-[(trichloro-2,2,2 dichloroacétamido-1 ) éthyl] dichloroacétamide (soit un rendement de 79,5%), de point de fusion 249-250°C.
Figure imgb0022
 10.2 g of dichloroacetamide (0.08 mole) are dissolved in 150 ml of chloroform. We add 10 g triethylamine (0.1 mole). Maintaining the temperature in the region of 0 ° C., 23.5 g of dissolved N - [(tetrachloro-1,2,2,2) ethyl] dichloroacetamide (0.08 mol) are added with stirring over approximately 1 hour. in 150 ml of chloroform. The mixture is allowed to return to ambient temperature with stirring, then it is taken up in 1 liter of water. After decantation, the organic phase is separated and washed twice with 500 ml of water, then dried over magnesium sulfate. The chloroform is distilled under vacuum and a solid is obtained which is recrystallized from hexane. 24.5 g of N - [(2,2,2-trichloro-dichloroacetamido-1) ethyl] dichloroacetamide are thus obtained (a yield of 79.5%), with a melting point of 249-250 ° C.

EXEMPLE N° 4EXAMPLE NO.4 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0023
Figure imgb0023

En opérant comme dans l'exemple No 1, mais en remplaçant les 14,75 g de chlorure de dichloroacétyle par 18,2 g de chlorure de trichloroacétyle (0,1 mole), on obtient 25,2 g (soit un rendement de 74,8%) de N-[(trichloro-2,2,2 trichloroacétamido-1 ) éthyl] formamide, de point de fusion 157-158°C.By operating as in Example No 1, but replacing the 14.75 g of dichloroacetyl chloride with 18.2 g of trichloroacetyl chloride (0.1 mole), 25.2 g are obtained (a yield of 74 , 8%) of N - [(2,2,2-trichloroacetamido-1) ethyl] formamide, m.p. 157-158 ° C.

EXEMPLE N° 5EXAMPLE NO.5 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0024
Figure imgb0024

En opérant comme dans l'exemple no 3, mais en remplaçant les 10,2 g de dichloroacétamide par 6,96 g d'isobutyramide (0,08 mole), on obtient 21 g (soit un rendement de 76,3%) de N-[(trichloro-2,2,2 dichloroacétamido-1 ) éthyl] isobutyramide de point de fusion 264-265°C.By operating as in Example No. 3, but replacing the 10.2 g of dichloroacetamide with 6.96 g of isobutyramide (0.08 mole), 21 g are obtained (representing a yield of 76.3%) of N - [(2,2,2-trichloro-1-dichloroacetamido) ethyl] isobutyramide with melting point 264-265 ° C.

EXEMPLE N° 6EXAMPLE NO.6 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0025
Figure imgb0025

On opère comme dans l'exemple 1, en remplaçant les 19,15 g de N-[(trichloro-2,2,2 amino-1) éthyl] formamide par 24,7 g de N-[(trichloro-2,2,2 amino-1) éthyl] trichloroacétamide (0,08 mole). On obtient ainsi 21,8 g (soit un rendement de 65%) de N-[(trichloro-2,2,2 dichloroacétamido-1) éthyl] trichloroacétamide de point de fusion 184-185°C.The procedure is as in Example 1, replacing the 19.15 g of N - [(2,2,2-trichloro-1 amino-1) ethyl] formamide with 24.7 g of N - [(2,2-trichloro) , 2 amino-1) ethyl] trichloroacetamide (0.08 mole). 21.8 g are thus obtained (ie a yield of 65%) of N - [(2,2,2-trichloro-dichloroacetamido-1) ethyl] trichloroacetamide with melting point 184-185 ° C.

Le N-[(trichloro-2,2,2 amino-1) éthyl] trichloroacétamide utilisé comme produit de départ peut être préparé comme suit:

  • On sature 300 ml de THF par de l'ammoniac gazeux et on maintient cette saturation pendant toute la durée de l'opération. En maintenant la température à 0°C, on ajoute sous agitation, en environ 1 h, 100 g de N-[(tétrachloro-1,2,2,2) éthyl] trichloroacétamide (0,3 mole). Le précipité de chlorure d'ammonium qui s'est formé est séparé par filtration. Le THF est ensuite séparé par distillation sous vide. On obtient ainsi 59 g de N-[(trichloro-2,2,2 amino-1) éthyl] trichloroacétamide (soit un rendement de 62,7%) sous la forme d'un solide blanc de point de fusion 132-133°C.
The N - [(2,2,2-trichloro-1 amino-1) ethyl] trichloroacetamide used as starting material can be prepared as follows:
  • 300 ml of THF are saturated with gaseous ammonia and this saturation is maintained throughout the duration of the operation. Maintaining the temperature at 0 ° C., 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide (0.3 mol) are added with stirring over approximately 1 hour. The precipitate of ammonium chloride which has formed is separated by filtration. THF is then separated by vacuum distillation. 59 g of N - [(2,2,2-amino-1 trichloro) ethyl] trichloroacetamide are thus obtained (ie a yield of 62.7%) in the form of a white solid with melting point 132-133 ° vs.

EXEMPLE N° 7EXAMPLE NO.7 Préparation du composé:.Compound preparation :.

Figure imgb0026
Figure imgb0026

On opère comme dans l'exemple 1, en remplaçant les 19,15 g de N-[(trichloro-2,2,2 amino-1) éthyl] formamide par 18,2 g de N-[(trichloro-2,2,2 amino-1) éthyl] o-chlorobenzamide (0,06 mole) et en utilisant 10,3 g de chlorure de dichloroacétyle (0,07 mole) au lieu de 14,75 g. On obtient ainsi, après évaporation du solvant, 23 g (soit un rendement de 79,5%) de N-[(trichloro-2,2,2 dichloroacétamido-1) éthyl] o-chlorobenzamide de point de fusion 214―215°C.The procedure is as in Example 1, replacing the 19.15 g of N - [(2,2,2-trichloro-1 amino-1) ethyl] formamide with 18.2 g of N - [(2,2-trichloro) , 2 amino-1) ethyl] o-chlorobenzamide (0.06 mole) and using 10.3 g of dichloroacetyl chloride (0.07 mole) instead of 14.75 g. 23 g (ie a yield of 79.5%) of N - [(2,2,2-trichloroacetamido-1) ethyl] o-chlorobenzamide with a melting point of 214―215 ° are thus obtained, after evaporation of the solvent. vs.

Le N-[(trichloro-2,2,2 amino-1) éthyl] o-chlorobenzamide utilisé comme produit de départ peut être préparé comme suit:

  • On opère comme pour la préparation du N-[(trichloro-2,2,2 amino-1) éthyl] trichloroacétamide mais en remplaçant les 100 g de N-[(tétrachloro-1,2,2,2) éthyl] trichloroacétamide par 100 g de N-[(tétrachloro-1,2,2,2) éthyl] o-chlorobenzamide (0,31 mole). On obtient 89 g (soit un rendement de 94,7%) de N-[(trichloro-2,2,2 amino-1) éthyl] o-chlorobenzamide, solide blanc de point de fusion 169-170°C.
The N - [(2,2,2-trichloro-1 amino-1) ethyl] o-chlorobenzamide used as starting material can be prepared as follows:
  • The operation is carried out as for the preparation of N - [(2,2,2-trichloro-1 amino-1) ethyl] trichloroacetamide but replacing the 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide with 100 g of N - [(tetrachloro-1,2,2,2) ethyl] o-chlorobenzamide (0.31 mole). 89 g (a yield of 94.7%) of N - [(2,2,2-trichloro-1-amino) ethyl] o-chlorobenzamide, a white solid with a melting point of 169-170 ° C., are obtained.

EXEMPLE N° 8EXAMPLE 8 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0027
Figure imgb0027

On dissout 24 g de N-[(dichloro-2,2 amino-1 ) éthyl] dichloroacétamide (0,1 mole) dans 300 ml de tétrahydrofuranne (THF). On ajoute 10,1 g de triéthylamine (0,1 mole). En maintenant la température à 20―25°C, on ajoute sous agitation, en environ 15 minutes, 17,5 g de chlorure d'o-chlorobenzoyle (0,1 mole) dissous dans 50 ml de THF. On maintient ensuite 1 heure sous agitation en laissant revenir à la température ambiante. On filtre le précipité de chlorhydrate de triéthylamine. On sépare le THF par distillation sous vide. On obtient un solide brun qui est recristallisé dans un mélange tétrachlorure de carbone-hexane 50/50. On obtient ainsi 15,3 g (soit un rendement de 40,4%) de N-[(dichloro-2,2 dichloroacétamido-1) éthyll o-chlorobenzamide de point de fusion 179-180°C.24 g of N - [(2,2-dichloro-1 amino-ethyl) ethyl] dichloroacetamide (0.1 mol) are dissolved in 300 ml of tetrahydrofuran (THF). 10.1 g of triethylamine (0.1 mole) are added. Maintaining the temperature at 20 ° -25 ° C., 17.5 g of o-chlorobenzoyl chloride (0.1 mol) dissolved in 50 ml of THF are added, with stirring, in approximately 15 minutes. Then maintained for 1 hour with stirring while allowing to return to room temperature. The precipitate of triethylamine hydrochloride is filtered. The THF is separated by vacuum distillation. A brown solid is obtained which is recrystallized from a 50/50 carbon tetrachloride-hexane mixture. 15.3 g are thus obtained (ie a yield of 40.4%) of N - [(2,2-dichloro-dichloroacetamido-1) ethyll o-chlorobenzamide, melting point 179-180 ° C.

Le N-[(dichloro-2,2 amino-1) éthyl] dichloroacétamide utilisé comme produit de départ peut être préparé comme indiqué à l'exemple 14.The N - [(2,2-dichloro-1 amino-1) ethyl] dichloroacetamide used as starting material can be prepared as indicated in Example 14.

EXEMPLE N° 9EXAMPLE NO.9 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0028
Figure imgb0028

On opère comme dans l'exemple 8, en remplaçant les 17,5 g de chlorure d'o-chlorobenzoyle par 11 g de chlorure d'isobutyryle (0,103 mole). On obtient ainsi 17,7 g (soit un rendement de 57,1 %) de N-[(dichloro-2,2-isobutyramido-1) éthyl] dichloracétamide de point de fusion 189-190°C.The procedure is as in Example 8, replacing the 17.5 g of o-chlorobenzoyl chloride with 11 g of isobutyryl chloride (0.103 mole). 17.7 g are thus obtained (ie a yield of 57.1%) of N - [(2,2-dichloro-2,2-isobutyramido-1) ethyl] dichloroacetamide with melting point 189-190 ° C.

EXEMPLE N° 10EXAMPLE 10 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0029
Figure imgb0029

On opère comme dans l'exemple 8, en remplaçant les 17,5 g de chlorure d'o-chlorobenzoyle par 10 g de chlorure d'acryloyle (0,11 mole). On obtient ainsi 12,8 g (soit un rendement de 43,5%) de N-[(dichloro-2,2 acrylamido-1 ) éthyl] dichloroacétamide.The procedure is as in Example 8, replacing the 17.5 g of o-chlorobenzoyl chloride with 10 g of acryloyl chloride (0.11 mole). 12.8 g are thus obtained (a yield of 43.5%) of N - [(2,2-dichloro-1-acrylamido) ethyl] dichloroacetamide.

EXEMPLE N° 11EXAMPLE 11 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0030
Figure imgb0030

On dissout 6,4 g de dichloroacétamide (0,05 mole) dans 50 ml de THF. On ajoute 7 g de triéthylamine (0,07 mole). En maintenant la température à 0°C, on ajoute sous agitation, en environ 15 minutes, 12,3 g de N-[(trifluoro-2,2,2-chloro-1) éthyl] dichloroacétamide (0,05 mole) dissous dans 20 ml de THF. On maintient ensuite trois heures sous agitation en laissant revenir à la température ambiante. On filtre le chlorhydrate de triéthylamine. Le THF est éliminé par distillation sous vide. On obtient ainsi 15 g (soit un rendement de 89%) de N-[(trifluoro-2,2,2 dichloroacétamido-1) éthyl] dichloroacétamide sous la forme d'un liquide visqueux brun.6.4 g of dichloroacetamide (0.05 mole) are dissolved in 50 ml of THF. 7 g of triethylamine (0.07 mole) are added. Maintaining the temperature at 0 ° C, added with stirring, in about 15 minutes, 12.3 g of N - [(trifluoro-2,2,2-chloro-1) ethyl] dichloroacetamide (0.05 mole) dissolved in 20 ml of THF. Then stirred for three hours while allowing to return to room temperature. The triethylamine hydrochloride is filtered. THF is removed by vacuum distillation. 15 g (a yield of 89%) of N - [(2,2,2-trifluoro-dichloroacetamido-1) ethyl] dichloroacetamide are thus obtained in the form of a brown viscous liquid.

Le N-[(trifluoro-2,2,2 chloro-1 ) éthyl] dichloroacétamide utilisé comme produit de départ peut être préparé comme suit:

  • On dissout dans 150 ml de benzène 19,2 g de dichloroacétamide (0,15 mole) et on ajoute, en 15 minutes environ, 22 g d'hydrate de fluoral (0,2 mole) et 1 ml d'acide sulfurique. On porte à reflux pendant 6 h sous agitation. Après refroidissement et filtration, on obtient 26,5 g de N-[(trifluoro-2,2,2 hydroxy-1) éthyl] dichloroacétamide (soit un rendement de 78%), sous la forme d'un solide blanc de point de fusion 70-71 °C.
The N - [(2,2,2-trifluoro-1 chloro-1) ethyl] dichloroacetamide used as starting material can be prepared as follows:
  • 19.2 g of dichloroacetamide (0.15 mole) are dissolved in 150 ml of benzene and 22 g of fluorine hydrate (0.2 mole) and 1 ml of sulfuric acid are added over approximately 15 minutes. The mixture is brought to reflux for 6 h with stirring. After cooling and filtration, 26.5 g of N - [(2,2,2-trifluoro-1-hydroxy) ethyl] dichloroacetamide are obtained (ie a yield of 78%), in the form of a white solid with a point of melting 70-71 ° C.

Dans un réacteur de 100 ml, on introduit sous agitation 5,5 g de N-[(trifluoro-2,2,2 hydroxy-1) éthyl] dichloroacétamide (0,025 mole) et 7,5 g de chlorure de thionyle (0,06 mole). On porte à reflux pendant 3 heures, puis on ajoute 30 ml d'hexane pour faciliter la précipitation au cours du refroidissement. Après filtration, on obtient 4,4 g de N-[(trifluoro-2,2,2 chloro-1) éthyl] dichloroacétamide (soit un rendement de 72%), sous la forme d'un solide blanc de point de fusion 54-55°C.5.5 g of N - [(2,2,2-trifluoro-1) ethyl] dichloroacetamide (0.025 mole) and 7.5 g of thionyl chloride (0, 0) are introduced into a 100 ml reactor. 06 mole). The mixture is refluxed for 3 hours, then 30 ml of hexane are added to facilitate precipitation during cooling. After filtration, 4.4 g of N - [(2,2,2-trifluoro-1-chloro) ethyl] dichloroacetamide are obtained (ie a yield of 72%), in the form of a white solid with melting point 54 -55 ° C.

EXEMPLE N° 12EXAMPLE 12 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0031
Figure imgb0031

En opérant comme à l'exemple 1, mais en remplaçant le N-[(trichloro-2,2,2 amino-1) éthyl] formamide par le N-[(trichloro-2,2,2 amino-1) éthyl] acétamide, on obtient, avec un rendement de 61,5% le N-[(trichloro-2,2,2, dichloroacétamido-1) éthyl] acétamide, de point de fusion 239-240° C.By operating as in Example 1, but replacing N - [(2,2,2-trichloro-1,2 amino-1) ethyl] formamide by N - [(2,2,2-trichloro-amino-1) ethyl] acetamide, N - [(2,2,2-trichloro-1-dichloroacetamido) ethyl] acetamide is obtained with a yield of 61.5%, melting point 239-240 ° C.

Le N-[(trichloro-2,2,2 amino-1) éthyl] acétamide utilisé comme produit de départ est préparé suivant la méthode employée pour préparer le N-[(trichloro-2,2,2 amino-1) éthyl] trichloroacétamide, mais en remplaçant les 100 g de N-[(tétrachloro-1,2,2,2) éthyl] trichloroacétamide par 320 g de N-[(tétrachloro-1,2,2,2) éthyl] acétamide (1,42 mole). L'addition au THF saturé d'ammoniac s'effectue en 1 h 45'. On obtient 262 g de N-[(trichloro-2,2,2 amino-1) éthyl]acétamide (soit un rendement de 89,6%), sous la forme d'un solide blanc de point de fusion 134-135°C.The N - [(2,2,2-trichloro-1 amino-1) ethyl] acetamide used as a starting product is prepared according to the method used to prepare the N - [(2,2,2-trichloro-1 amino) ethyl] trichloroacetamide, but by replacing the 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide with 320 g of N - [(tetrachloro-1,2,2,2) ethyl] acetamide (1, 42 mole). The addition to THF saturated with ammonia is carried out in 1 h 45 '. 262 g of N - [(2,2,2-amino-1 trichloro) ethyl] acetamide are obtained (ie a yield of 89.6%), in the form of a white solid with melting point 134-135 ° vs.

EXEMPLE N° 13EXAMPLE 13 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0032
Figure imgb0032

En opérant comme à l'exemple 8, mais en remplaçant le chlorure d'o-chlorobenzoyle par le chlorure de p-méthoxybenzoyle, on obtient, avec un rendement de 70,9%, le N-[(dichloro-2,2 dichloroacétamido-1 ) éthyl] p-méthoxybenzamide, de point de fusion 171-172°C.By operating as in Example 8, but replacing the o-chlorobenzoyl chloride with p-methoxybenzoyl chloride, the N - [(2,2-dichloroacetamido) is obtained with a yield of 70.9% -1) ethyl] p-methoxybenzamide, mp 171-172 ° C.

EXEMPLE N° 14EXAMPLE 14 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0033
Figure imgb0033

On dissout dans 60 ml de benzène 64 g de dichloroacétamide (0,5 mole) et on ajoute, en 10 minutes environ, 68 g de dichloroacétaldéhyde (0,6 mole) et 1 ml d'acide sulfurique. On porte à reflux pendant 5 heures et on évapore le solvant et l'excès de dichloroacétaldéhyde sous vide. On obtient ainsi 118 g de N-[(dichloro-2,2 hydroxy-1 ) éthyl] dichloroacétamide brut (soit un rendement de 98%), sous la forme d'un liquide visqueux pratiquement incolore.

Figure imgb0034
64 g of dichloroacetamide (0.5 mole) are dissolved in 60 ml of benzene and 68 g of dichloroacetaldehyde (0.6 mole) and 1 ml of sulfuric acid are added over approximately 10 minutes. The mixture is refluxed for 5 hours and the solvent and the excess of dichloroacetaldehyde are evaporated in vacuo. 118 g of N - [(2,2-dichloro-1 hydroxy-1) ethyl] crude dichloroacetamide are thus obtained (ie a yield of 98%), in the form of a practically colorless viscous liquid.
Figure imgb0034

Dans un réacteur de 500 ml, on introduit sous agitation 210 g de N-[(dichloro-2,2 hydroxy-1) éthyl] dichloroacétamide (0,87 mole) préparé comme indiqué ci-dessus et 300 g de chlorure de thionyle (2,5 moles). On porte à reflux pendant 2 h 30'. On ajoute 300 ml d'hexane pour faciliter la précipitation au cours du refroidissement. Après filtration, on obtient 175 g de N-[(trichloro-2,2,1) éthyl] dichloroacétamide (soit un rendement de 77,5%), sous la forme d'un solide blanc de point de fusion 77-78°C.210 g of N - [(2,2-dichloro-1-hydroxy) ethyl] dichloroacetamide (0.87 mole) prepared as indicated above and 300 g of thionyl chloride are introduced into a 500 ml reactor, with stirring. 2.5 moles). The mixture is brought to reflux for 2 h 30 '. 300 ml of hexane are added to facilitate precipitation during cooling. After filtration, 175 g of N - [(2,2,2-trichloro) ethyl] dichloroacetamide (ie a yield of 77.5%) are obtained in the form of a white solid with melting point 77-78 °. vs.

On sature 600 ml de THF par de l'ammoniac gazeux et on maintient cette saturation pendant toute la durée de l'opération suivante. En maintenant la température à 0°C, on ajoute sous agitation, en environ 1 heure, 130 g de N-[(trichloro-2,2,1) éthyl] dichloroacétamide (0,5 mole) préparé comme indiqué ci-dessus. Le chlorure d'ammonium formé est séparé par filtration. Le THF est ensuite évaporé sous vide. On obtient ainsi 95,4 g de N-[(dichloro-2,2 amino-1 )éthyl] dichloroacétamide (soit un rendement de 79,5%) sous la forme d'un solide blanc de point de fusion 96-97°C.600 ml of THF are saturated with gaseous ammonia and this saturation is maintained for the duration of the following operation. Maintaining the temperature at 0 ° C., 130 g of N - [(2,2,2-trichloro) ethyl] dichloroacetamide (0.5 mol) prepared as indicated above are added with stirring over approximately 1 hour. The ammonium chloride formed is separated by filtration. THF is then evaporated in vacuo. 95.4 g of N - [(2,2-dichloro-1 amino-1) ethyl] dichloroacetamide are thus obtained (ie a yield of 79.5%) in the form of a white solid with melting point 96-97 °. vs.

EXEMPLE N° 15EXAMPLE 15 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0035
Figure imgb0035

En opérant à l'exemple 3, mais en replaçant le dichloroacétamide et le N-[(tétrachloro-1 ,2,2,2) éthyl] dichloroacétamide par respectivement le formamide et le N-[(trichloro-1,2,2) éthyl] dichloroacétamide, on obtient, avec un rendement de 74,6%, le N―[(dichloro-2,2 dichloroacétamido-1 ) éthyl] formamide, de point de fusion 79-80oC.By operating in Example 3, but by replacing the dichloroacetamide and the N - [(tetrachloro-1, 2,2,2) ethyl] dichloroacetamide by respectively the formamide and the N - [(trichloro-1,2,2) ethyl] dichloroacetamide, N - [(2,2-dichloroacetamido-1) ethyl] formamide, with melting point 79-80 o C., is obtained with a yield of 74.6%.

EXEMPLE N° 16EXAMPLE 16 Préparation du composé de formule:Preparation of the compound of formula:

Figure imgb0036
Figure imgb0036

En opérant comme à l'exemple 3, mais en remplaçant le dichloroacétamide et le N-[(tétrachloro-1,2,2,2) éthyl] dichloroacétamide par respectivement l'acétamide et le N-[(trichloro-1,2,2) éthyl] dichloroacétamide, on obtient, avec un rendement de 78%, le N-[(dichloro-2,2 dichloroacétamido-1 ) éthyl] acétamide, de point de fusion 63-64°C.By operating as in Example 3, but replacing the dichloroacetamide and the N - [(tetrachloro-1,2,2,2) ethyl] dichloroacetamide by acetamide and the N - [(1,2-trichloro, respectively) 2) ethyl] dichloroacetamide, N - [(2,2-dichloroacetamido-1) ethyl] acetamide, melting point 63-64 ° C., is obtained with a yield of 78%.

EXEMPLE N° 17EXAMPLE 17 Activité antidote d'herbicides des composés selon l'invention.Antidote activity of herbicides of the compounds according to the invention.

Un sol, constitué de deux parties en poids d'argile et trois parties en poids de sable, est épandu dans des barquettes en plastique de dimensions 18 x 12 x 5 cm. Sur ce soi on sème, selon 4 sillons de 0,5 cm de profondeur, 10 graines de maïs, variété "Sandrina", et 10 graines d'orge, variété "Rika."A soil, consisting of two parts by weight of clay and three parts by weight of sand, is spread in plastic tubs of dimensions 18 x 12 x 5 cm. On this seed we sow, in 4 furrows of 0.5 cm deep, 10 corn seeds, variety "Sandrina", and 10 barley seeds, variety "Rika."

Les semis ainsi réalisés sont séparés en 3 lots, chaque lot contenant 5 barquettes. Sur le ler lot on répand une couche, de 2cm d'épaisseur, d'une terre n'ayant subi aucun traitement. Sur le 2ème lot on répand une couche, d'épaisseur 2 cm, d'une terre dans laquelle on a incorporé par brassage soigné un herbicide naturellement phytotoxique pour le maïs à la dose où il est appliqué. Enfin, sur le 3ème lot, on répand une couche, d'épaisseur 2 cm, d'une terre dans laquelle on a incorporé le même herbicide que pour le 2ème lot, à la même dose, et un produit antidote selon l'invention.The seedlings thus produced are separated into 3 batches, each batch containing 5 trays. On the 1st batch spread a layer, 2cm thick, of soil that has not undergone any treatment. On the 2nd batch spread a layer, 2 cm thick, of soil in which we have incorporated by careful mixing a naturally phytotoxic herbicide for corn at the dose where it is applied. Finally, on the 3rd batch, spread a layer, 2 cm thick, of soil in which the same herbicide has been incorporated as for the 2nd batch, at the same dose, and an antidote product according to the invention.

Pour leur incorporation dans la terre l'herbicide et le produit antidote sont formulés sous forme de suspensions aqueuses. Les quantités d'herbicide apportées correspondent à des doses d'herbicides de 5 kg et 10 kg/ha. Les quantités de produit antidote apportées correspondent à des doses égales au dixième des doses de l'herbicide, soit 0,5 et 1 kg/ha. L'herbicide utilisé est l'E.P.T.C. ou N,N-dipropyl thiolcarbamate d'éthyle. Les produits antidote testés sont les composés des exemples 1 à 15.For their incorporation into the soil the herbicide and the antidote are formulated in the form of aqueous suspensions. The quantities of herbicide applied correspond to doses of herbicides of 5 kg and 10 kg / ha. The amounts of antidote product provided correspond to doses equal to one tenth of the doses of the herbicide, ie 0.5 and 1 kg / ha. The herbicide used is E.P.T.C. or N, N, ethyl dipropyl thiolcarbamate. The antidote products tested are the compounds of Examples 1 to 15.

Les lots de barquettes, une fois traités, sont placés dans une serre maintenue à 20°C et à un taux d'hygrométrie de 70%. 12 et 20 jours après le traitement (J + 12; J + 20), les lots sont examinés et on détermine d'une part l'efficacité herbicide de l'association "antidote + herbicide," d'autre part l'efficacité antidote du composé selon l'invention testé. L'efficacité antidote E est évaluée en mesurant la hauteur moyenne des plants de maïs dans les trois lots. Elle est donnée par la formule:

Figure imgb0037
dans laquelle A désigne la taille moyenne des plants de maïs dans les lots témoins non traités, B la taille moyenne des plants de maïs dans les lots traités avec l'herbicide seul et C la taille moyenne des plants de maïs dans les lots traités avec l'herbicide et le produit antidote. Une efficacité antidote égale à 0 correspond donc à C = B et une efficacité antidote égale à 100 correspond à C = A.The batches of trays, once treated, are placed in a greenhouse maintained at 20 ° C and at a humidity rate of 70%. 12 and 20 days after the treatment (D + 12; D + 20), the batches are examined and the herbicidal efficacy of the “antidote + herbicidal combination” is determined on the one hand and on the other hand the antidote efficacy of the compound according to the invention tested. Antidote E efficacy is evaluated by measuring the average height of the maize plants in the three batches. It is given by the formula:
Figure imgb0037
 in which A denotes the average size of the corn plants in the untreated control lots, B the average size of the corn plants in the lots treated with the herbicide alone and C the average size of the corn plants in the lots treated with l herbicide and antidote. An antidote efficiency equal to 0 therefore corresponds to C = B and an antidote efficiency equal to 100 corresponds to C = A.

On constate que, dans tous les essais réalisés avec les associations "antidote + herbicide" à faible dose ou à forte dose, les orges, qui servent ici de plantes adventices de référence, sont détruite à 100%, ce qui prouve que l'efficacité herbicide vis-à-vis des graminacées n'est pas réduite par les produits selon l'invention.It can be seen that, in all the tests carried out with the low-dose or high-dose “antidote + herbicide” associations, the barley, which is used here as reference weed plants, is 100% destroyed, which proves that the effectiveness herbicide with respect to gramineae is not reduced by the products according to the invention.

Les résultats concernant l'efficacité antidote E sont rassemblés dans le tableau de la page 20.The results concerning the antidote E efficacy are collated in the table on page 20.

On voit que les composés des exemples 1, 3, 4, 9, 11 et 14, associés à l'E.P.T.C., ont une efficacité antidote particulièrement marquéeWe see that the compounds of Examples 1, 3, 4, 9, 11 and 14, associated with the E.P.T.C., Have a particularly marked antidote efficacy.

EXEMPLE ? 18EXAMPLE? 18 Activité antidote d'herbicide du composé de l'exemple 1.Antidote activity of herbicide of the compound of Example 1.

Dans le présent essai, le produit de l'exemple 1 a été testé suivant la méthode décrite dans l'exemple précédent, mais en faisant varier la dose du produit antidote par rapport à celle de l'herbicide associé (EPTC).In the present test, the product of Example 1 was tested according to the method described in the previous example, but by varying the dose of the antidote product relative to that of the associated herbicide (EPTC).

L'herbicide a été appliqué à la dose de 5 kg/ha et le produit de l'exemple 1 aux doses 0 kg/ha (essais avec herbicide seul), 0,312 kg/ha, 0,625 kg/ha, 1,250 kg/ha et 2,500 kg/ha.The herbicide was applied at the dose of 5 kg / ha and the product of Example 1 at the doses 0 kg / ha (tests with herbicide alone), 0.312 kg / ha, 0.625 kg / ha, 1.250 kg / ha and 2,500 kg / ha.

Les notations, effectuées au jour J + 20, ont donné pour l'efficatité antidote E les résultats du tableau ci-dessous:

Figure imgb0038
The ratings, carried out on day D + 20, gave the results in the table below for the antidote E effectiveness:
Figure imgb0038

Ce tabelau montre que l'efficacité antidote croit avec la dose du composé de l'exemple 1 et que ce composé ne présente pas de phytotoxicité vis-à-vis du maïs, même à la dose la plus élevée.This table shows that the antidote efficiency increases with the dose of the compound of Example 1 and that this compound does not exhibit phytotoxicity with respect to corn, even at the highest dose.

Quant au pouvoir herbicide de l'EPTC vis-à-vis des plantes adventices (orge), il n'est pas réduit par les doses croissantes de composé antidote.

Figure imgb0039
As for the herbicidal power of the EPTC vis-à-vis weeds (barley), it is not reduced by the increasing doses of antidote compound.
Figure imgb0039

Claims (17)

1. A process for the treatment of cultivated crops in order to protect them against the damage caused by herbicides belonging to the chloroacetanilide, urea, triazine, carbamate, uracil and thiolcarbamate families, which comprises applying to the cultivated surface before or after the emergence of the crop, before or after the application of the herbicide or at the same time as the latter, or to the seeds of the crops, a compound which is an antidote to the herbicides corresponding to the formula:
Figure imgb0050
in which R1 represents a dichloromethyl or trichloromethyl group, X, represents a chlorine or fluorine atom, X2 represents a chlorine or fluorine atom, X3 represents a hydrogen, chlorine or fluorine.atom, R2 represents an amino group NH2 or an
Figure imgb0051
group where R3 represents a hydrogen atom or an alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, cycloalkyl, halocycloalkyl, alkoxy, alkyl, haloalkoxyalkyl or aryl group, this latter being possibly substituted by one or two halogen atoms or by an alkyl, alkoxy, nitro or haloalkyl group.
2. A process according to claim 1, in which the herbicide belongs to the thiolcarbamate family.
3. A process according to claim 2, in which the herbicide is ethyl N,N-dipropyl-thiolcarbamate.
4. A process according to anyone of the claims 2 and 3, in which the compound of formula (I) is selected from N-[(2,2,2-trichloro-1-dichloroacetamido)-ethyl]-formamide, N-[(2,2,2-trichloro-1-dichloroacetamido-ethyl]-dichloroacetamide, N-[(2,2-dichloro-1-isobutyramido)-ethyl]-dichloro- acetamide and N-[(2,2,2-trifluoro-1-dichloroacetamido)-ethyl]-dichloroacetamide.
5. Compounds of the formula:
Figure imgb0052
in which R1 represents a dichloromethyl or trichloromethyl group, X1 represents a chlorine or fluorine atom, X2 represents a chlorine of fluorine atom, X3 represents a hydrogen, chlorine or fluorine atom and R2 represents an amino NH2 group.
6. Compounds corresponding to formula (I) of claim 1 for which X1, X2, X3 are not all three chlorine atoms and R2 is a
Figure imgb0053
group, R3 being as defined in claim 1.
7. Compounds according to claim 6, in which, in the definition of R3' the alkyl and alkoxy chains of the alkyl, haloalkyl, arylalkyl, arylhaloalkyl, alkoxyalkyl, and haloalkoxyalkyl groups have 1 to 5 carbon atoms, the alkenyl chains of the alkenyl and haloalkenyl groups have 2 to 5 carbon atoms, the cycloalkyl and halocycloalkyl groups have 3 to 6 carbon atoms, the haloalkyl haloalkenyl, arylhaloalkyl, halocycloalkyl, and haloalkoxyalkyl groups have 1 to 7 halogen atoms taken from the chlorine, bromine or fluorine atoms, aryl denotes phenyl and the halogen substituent of the aryl group is a chlorine atom.
8. Compounds according to claim 7, in which R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms and 1 to 7 halogen atoms or a phenyl group substituent by one or two chlorine atoms.
9. Compounds according to claim 8, in which
Figure imgb0054
is a formamido, acetamido, isobutyramido, acrylamido, dichloroacetamido, or o-chlorobenzamido group.
10. The compound N-[(2,2-dichloro-1-isobutyramido)-ethyl]-dichloroacetamide.
11. The compound N-[(2,2,2-trifluoro-1-dichloroacetamido)-ethyl]-dichloroacetamide.
12. A process for the preparation of the compounds according to claim 5, in which a chlorinated derivative of the formula:
Figure imgb0055
in which R1, X1, X2 and X3 have the same significance as in claim 1, is reacted with ammonia.
13. A process according to claim 12, in which the reaction is effected in an inert solvent, at a temperature between -30°C and +30°C.
14. A process for the preparation of the compounds according to claim 6, in which an amino compound of the formula:
Figure imgb0056
in which R1, R3, X1, X2, X3 are as defined in claim 1 and X1, X2, X3 are not all three chlorine atoms, is reacted with respectively an acid chloride of formula
Figure imgb0057
in which R3 and R1 are as defined in claim 1.
15. A process according to claim 14, in which the reaction is effected in an inert solvent, at a temperature between -30°C and +60°C and in the presence of a mineral base or a tertiary amine.
16. A process for the preparation of the compounds according to claim 6, in which a chlorine derivative of the formula:
Figure imgb0058
in which R1, R3' X1, X2, X3 are as defined in claim 1 and X1, X2, X3 are not all three chlorine atoms, is reacted respectively with an amide of formula
Figure imgb0059
in which R3 and R1 are as defined in claim 1.
17. A process according to claim 16, in which the reaction is effected in an inert solvent, at a temperature between -30°C and +60°C and in the presence of a mineral base or a tertiary amine.
EP78400063A 1977-08-03 1978-07-21 Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation Expired EP0000852B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7723866 1977-08-03
FR7723866A FR2399408A1 (en) 1977-08-03 1977-08-03 DICHLOROACETAMIDE AND TRICHLOROACETAMIDE DERIVATIVES HERBICIDE ANTIDOTES

Publications (2)

Publication Number Publication Date
EP0000852A1 EP0000852A1 (en) 1979-02-21
EP0000852B1 true EP0000852B1 (en) 1982-08-25

Family

ID=9194171

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78400063A Expired EP0000852B1 (en) 1977-08-03 1978-07-21 Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation

Country Status (11)

Country Link
US (1) US4330323A (en)
EP (1) EP0000852B1 (en)
BR (1) BR7804963A (en)
CA (1) CA1116632A (en)
DE (1) DE2862004D1 (en)
DK (1) DK314678A (en)
ES (1) ES472304A1 (en)
FR (1) FR2399408A1 (en)
IT (1) IT1172893B (en)
PT (1) PT68222A (en)
RO (1) RO76179A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU183997B (en) * 1982-07-14 1984-06-28 Noevenyvedelmi Kutato Intezet Herbicide and antidote composition resp. containing thiolcarba mate derivative and/or chloroacetanilide derivatives as herbicide and/or substituted acetamide antidote
JPS61293956A (en) * 1985-06-21 1986-12-24 Tokuyama Soda Co Ltd Chloroacetamide compound and production thereof
US5201933A (en) * 1988-08-01 1993-04-13 Monsanto Company Safening herbicidal benzoic acid derivatives

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1617457U (en) 1950-11-07 1950-12-14 Anton Grimm CLOTHING HANGER.
US2742501A (en) * 1951-06-11 1956-04-17 Glanzstoff Ag Method of producing alkylidene bis-amides
DE1186467B (en) * 1963-01-25 1965-02-04 Bayer Ag Process for the preparation of acylated beta, beta, beta-trichloroacetaldehyde aminals
GB1054347A (en) * 1964-10-29
DE1617459A1 (en) * 1966-03-18 1971-04-08 Bayer Ag Amidal halogenated aliphatic aldehydes
BE756062A (en) * 1969-09-11 1971-03-11 Boehringer Sohn Ingelheim 1,1,1-TRICHLORETHANE DERIVATIVES THEIR MANUFACTURING PROCESSES AND THEIR USE AS BIOCIDAL SUBSTANCES
DE2047258A1 (en) * 1970-03-18 1971-10-07 VEB Chemiekombinat Bitterfeld, χ 4400 Bitterfeld Unsymmetrical n,n-trichloroethylidene-bis-amides
DD105113A1 (en) 1973-01-31 1974-04-12
US3923494A (en) * 1973-05-24 1975-12-02 Stauffer Chemical Co Gem-bis amide herbicide antidote compositions and methods of use
DE2358592A1 (en) 1973-11-24 1975-06-05 Bayer Ag ANTIMICROBIAL AGENTS
US4146646A (en) * 1976-02-12 1979-03-27 Fisons Limited Bis-amide fungicidal compounds

Also Published As

Publication number Publication date
IT1172893B (en) 1987-06-18
ES472304A1 (en) 1979-10-01
CA1116632A (en) 1982-01-19
RO76179A (en) 1982-04-12
BR7804963A (en) 1979-03-13
EP0000852A1 (en) 1979-02-21
DK314678A (en) 1979-02-04
PT68222A (en) 1978-07-01
FR2399408A1 (en) 1979-03-02
DE2862004D1 (en) 1982-10-21
FR2399408B1 (en) 1980-03-21
US4330323A (en) 1982-05-18
IT7868804A0 (en) 1978-07-28

Similar Documents

Publication Publication Date Title
CA1087183A (en) Heterocyclic derivatives as antidotes against herbicids
FR2460936A1 (en) PYRIDAZINE DERIVATIVES AND THEIR APPLICATION AS FUNGICIDES
FR2518547A1 (en) SUBSTITUTED PROPIONIC-2 PHENOXY ACID DERIVATIVES AND THEIR USE AS HERBICIDES
EP0000852B1 (en) Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation
FR2568749A1 (en) COMPOSITION BASED ON THIOLCARBAMATE DERIVATIVE, METHOD FOR EXTENDING HERBICIDE ACTION, AND HERBICIDAL COMPOSITIONS HAVING PROLONGED ACTION
US4008067A (en) Oxacyclohexane derivatives
FR2491061A1 (en) COMPOUNDS FOR REGULATING PLANT GROWTH AND PROCESS FOR PREPARING THE COMPOUNDS
FR2582647A1 (en) PHENANTHRENE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND FUNGICIDE COMPOSITIONS CONTAINING SAME
FR2495609A1 (en) ACYLUREES, PROCESSES FOR THEIR PREPARATION AND INSECTICIDAL PRODUCTS CONTAINING SUCH COMPOUNDS
US4900350A (en) 5-Iminomethyl-halo-acyloxazolidines having an inhibiting action on the phytotoxicity of herbicides
EP0239508A2 (en) 2-Cyano-benzimidazole derivatives, their preparation and use as fungicides, their association with other fungicides
CA1325810C (en) Cyanoacetamido-derivatives having a fungicidal activity
US4288384A (en) N-Cyanoalkyl haloacetamides herbicidal antidotes
US4650516A (en) α-halo-Ω-haloalkylamides herbicidal antidotes
CH554886A (en) Herbicidal and fungicidal 1-(1,3,4-thiadiazol-2-yl)-3-substd. ureas - prepd. from 2-amino-5-substd.-1,3,4-thiadiazoles and N,N'-carbonyldiimidazole
FR2555579A1 (en) NOVEL DERIVATIVES OF PYRIDYLACETONITRILES, THEIR PREPARATION AND THEIR USE AS ANTIFUNGAL IN THE AGRICULTURAL FIELD
FR2462430A1 (en) NOVEL 1,2,4-TRIAZOLIDINE-3,5-DITHIONES TRISUBSTITUTED IN POSITIONS 1, 2 AND 4, COMPOSITION CONTAINING SAME AND USE THEREOF AS HERBICIDES AND AS PLANT GROWTH SUBSTANCES
US3466164A (en) Process for the control of plant growth with n-(substituted benzylidene) alkyl amines
US4335053A (en) N-cyanobenzyl haloacetamides
EP0037527A1 (en) Substituted acetanilides, process for their preparation and their utilization as herbicides
LU86116A1 (en) SELECTIVE HERBICIDE COMPOSITIONS HAVING A PROLONGED ACTION AND CONTAINING, AS ACTIVE INGREDIENT, ALPHA-CHLORACETAMIDE DERIVATIVES
BE897291A (en) SUBSTITUTED ACETAMIDES HAVING ANTIDOTAL PROPERTIES, THEIR PREPARATION ANTIDOTAL COMPOSITIONS CONTAINING THESE COMPOUNDS AND SELECTIVE HERBICIDE COMPOSITIONS CONTAINING THESE ANTIDOTES
CH556862A (en) 1-(1,3,4-Thiadiazol-2-yl)-urea derivs as herbicides - and fungicides, prepd. from 2-amino-1,3,4-thiadiazoles
US4303792A (en) N-substituted haloacyloxyacetamides herbicidal antidotes
EP0021939A1 (en) Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB LU NL

17P Request for examination filed
DET De: translation of patent claims
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB LU NL

REF Corresponds to:

Ref document number: 2862004

Country of ref document: DE

Date of ref document: 19821021

GBPC Gb: european patent ceased through non-payment of renewal fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19830622

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19830731

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870731

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19900201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920624

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920702

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920930

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19930731

BERE Be: lapsed

Owner name: STAUFFER CHEMICAL B.V.

Effective date: 19930731

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940401

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970709

Year of fee payment: 20

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT