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EP0000681A1 - Amino-2 (or -4) alkylthio-5 pyrimidines, processes for their preparation, their use as herbicides and composition containing them - Google Patents

Amino-2 (or -4) alkylthio-5 pyrimidines, processes for their preparation, their use as herbicides and composition containing them Download PDF

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Publication number
EP0000681A1
EP0000681A1 EP78400062A EP78400062A EP0000681A1 EP 0000681 A1 EP0000681 A1 EP 0000681A1 EP 78400062 A EP78400062 A EP 78400062A EP 78400062 A EP78400062 A EP 78400062A EP 0000681 A1 EP0000681 A1 EP 0000681A1
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Prior art keywords
pyrimidine
methylthio
chloro
formula
compounds
Prior art date
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EP78400062A
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German (de)
French (fr)
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EP0000681B1 (en
Inventor
Daniel Balde
Gérard Emile Marcel Boutemy
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Produits Chimiques Ugine Kuhlmann
Pechiney SA
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Produits Chimiques Ugine Kuhlmann
Ugine Kuhlmann SA
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Priority claimed from FR7723222A external-priority patent/FR2398737A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms

Definitions

  • the present invention relates to novel 5-alkylthio-pyrimidines carrying an amino or acylamino group, their methods of preparation and their application as herbicides.
  • Herbicide pyrimidine derivatives are already known (see for example French patents 2,031,422, 2,317,291, 2,119,234, and 2,137,933), but these derivatives never simultaneously carry an alkylthio group in position 5 and a amino or acylamino group.
  • the new 5-alkylthio pyrimidines according to the invention can be represented by the general formula: in which R 1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X 1 , X 2 , X 3 is a chlorine or bromine atom, preferably a chlorine atom, and the other two are respectively groups wherein
  • R 2 and R 3 represent, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or R being a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, or together with the nitrogen atom to which they are attached form a heterocyclic nitrogen radical other than the piperazino and substituted piperazino radicals
  • R 4 and R 5 represent, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or R being as defined above, or together with the nitrogen atom to which they are linked form a heterocyclic nitrogen radical other than the piperazino and substituted piperazino radicals, at least one of the groups being an NH 2 group or
  • cycloalkyl is preferably cyclohexyl and aryl is preferably phenyl.
  • heterocyclic nitrogen radicals mention may be made of the piperidino, morpholino and 2,6-dimethyl morpholino radicals.
  • the present invention relates to the compounds of formula (I) as a whole, it relates more particularly to those of these compounds for which X 1 is a chlorine atom, one of the substituents X 2 and X 3 is a group NH 2 and the other is an NH 2 group, monoalkylamino or dialkylamino in which the alkyl chains have 1 to 5 carbon atoms, piperidino or morpholino.
  • the compounds of formula (I) in which R 2 , R 3 , R 4 , R 5 are not and in which therefore at least one of the groups is an NH 2 group can be prepared by condensation of a 2,4,6-trihalo-5-alkylthio pyrimidine of formula (II) with a compound of formula (III) and condensation of 4,6-dihalo (or-2 , 6) 5-alkylthio pyrimidine of formula (IV) or (IV) bis thus obtained with a compound of formula (V), according to the reaction scheme:
  • X is a chlorine or bromine atom and R 1 , R 2 , R 3 , R 4 and R have the same meanings as in formula (I), except, for R 2 to R 59 meaning At least one of the compounds (III) and (V) is therefore necessarily ammonia, m and n are numbers greater than 0 and less than 1.
  • 2,4,6-tilhalo-5,6-alkylthio pyrimidines of formula (II) are known products. They can be prepared for example by the process described in French patent 1,549,494 requested on October 31, 1967.
  • the condensation reactions (1), (2) and (2) bis can be carried out either in an aqueous medium, or in an organic solvent medium, or even in a mixed water + organic solvent medium.
  • organic solvents which can be used, mention may in particular be made, without being limiting, of toluene, methanol, aliphatic ketones such as acetone, methyl ethyl ketone or diethyl ketone, dimethylformamide or an excess of compound (III) or ( V), when the latter is an amine.
  • the condensation reactions (1), (2) and (2) bis are carried out in the presence of a basic agent capable of fixing the hydrohalic acid HX formed in the reaction.
  • a basic agent capable of fixing the hydrohalic acid HX formed in the reaction there may be mentioned, for example, alkali metal hydroxides, ammonia, or an excess of the compounds of formula (III) or (V).
  • Reactions (1), (2) and (2) bis are carried out at a temperature which depends in particular on the solvent used.
  • reaction (1) is carried out between 0 and 150 ° C. It can therefore be carried out at a temperature below the ordinary temperature, for example between 0 and 10 ° C, or at a temperature above the ordinary temperature, for example between 100 and 150 ° C.
  • Reactions (2) and (2) bis cannot be carried out at temperatures as lower than those usable for the reaction (1). They are generally carried out between 100 and 150 ° C.
  • reactions (1), (2) and (2) bis are carried out at atmospheric pressure or under a pressure higher than atmospheric pressure.
  • the ishalers (IV) and (IV) bis 5-alkylthio-pyrimidines dihalc obtained in reaction (1) can be separated, for example by fractional crystallization.
  • the isomers thus separated then provide, by reactions (2) and (2) bis, the pure compound (I) and the mixture of the two isomeric compounds (I) bis and (I) ter.
  • the mixture of compounds (IV) and (IV) bis obtained in reaction (1) can also be subjected to the second stage of the process [reaction with compound (V)].
  • a mixture of the three isomeric compounds (I), (I) bis, and (I) ter is then obtained, a mixture which can be used as it is in herbicidal applications.
  • the isomeric compounds (I), (I) bis and (I) ter can also be separated by preparative liquid chromatography.
  • the isomer (VI) is predominant (a less than 1 and greater than 0.5).
  • Reaction (4) which has the originality of selectively providing the 4,6-dihalo-5-alkylthio-pyrimidine isomer, can be carried out in an organic solvent medium, at a temperature between 100 and 150 "C.
  • organic solvent medium the same solvents can be mentioned as for reactions (1), (2) and (2) bis.
  • Reaction (5) is carried out under the same conditions as reaction (2).
  • the compounds formed in reactions (1), (2), (2) bis, (3), (4) and (5) can be isolated from the reaction medium by conventional methods such as, for example, filtration, when the compounds precipitate, or the distillation under reduced pressure of the solvent followed by washing the residue with water, and purified by recrystallization from an appropriate solvent.
  • the compounds of formula (I) in which at least one of the substituents R 2 , R 3 , R 4 , R 5 is a group can be prepared by acylation of the compounds of formula (I) in which R 2 , R 3 , R 4 , R 5 are not
  • This acylation is carried out using the usual acylating agents such as acid chlorides, acid anhydrides, ketene or homologous compounds.
  • the operation is carried out in an organic solvent medium, at a temperature between 20 and 120 ° C., preferably between 50 and 100 ° C.
  • organic solvents which can be used mention may in particular be made of carboxylic acids, in the case where the acylation is carried out with an acid anhydride, and pyridine, in the case where the acylation is carried out with an acid chloride.
  • the compounds of formula (I) can be transformed into their salts with mineral or organic acids by reaction with the corresponding acid in an appropriate solvent.
  • the compounds of formula (I) and their salts with mineral or organic acids have the property of destroying a large number of undesirable plants belonging to the classes of monocots or dicots and this at very low doses of between 150 g / ha and 2500 g / ha. In particular, they totally destroy the following plants: ryegrass, switchgrass, crabgrass, foxtail, wild oats, bedstraw, amaranth, knotweed, capsella, speedwell, mustard, datura, chickweed, stellar, thistle, fumitory, chenopoda, sorrel, plantain , atriclex, dandelion, poppy, chrysanthemum, senearme, milkweed, spurge.
  • the compounds of formula (I) and their salts generally have no unfavorable action on winter and spring cereals such as wheat and barley, on rice and corn.
  • the compounds of formula (I) and their salts are active with regard to weeds as well in pre-emergence treatments as in post-emergence treatments. However, their activity is more marked in post-emergence treatments.
  • the herbicidal compounds according to the invention can be incorporated, jointly with other herbicides or separately, in formulations which contain, in addition to the active material, the inert additives usually used in agriculture to facilitate the preservation, in aqueous suspension, adhesion to the foliage and resistance to atmospheric agents and biological degradation (hence greater persistence of the action), such as solid diluents (talc, silica, kieselguhr, clay, etc.) .) or liquids (mineral oils, water, organic solvents such as ketones, alcohols, hydrocarbons or their chlorinated derivatives), adjuvants, surfactants, antioxidants and stabilizers.
  • Such formulations can be in the form of wettable powders, solutions emulsifiable in water, suspensions, granules or any other form in use in the field of herbicides.
  • the content of compounds of formula (I) or their salts (active material) can vary from 1% to 95% by weight.
  • the content of compounds according to the invention can vary from 1% to 80% by weight, that in other herbicides from 80% to 1% by weight, the complement to 100 being constituted by inert additives.
  • EXAMPLE 2 Mixture of the three isomers of 4-amino-6-chloro-2-ethylamino-5-methylthio pyrimidine, 2-amino-6-chloro-4-ethylamino-5-methylthio-pyrimidine and 2-chloro-6 amino-4-ethylamino-5-pyrimidine.
  • the synthesis is carried out in 2 steps.
  • the procedure is as in the first step of Example 1, replacing the ethylamine with 11.5 B of isopropylamine.
  • the synthesis is carried out in two stages.
  • this mixture contains 50.3 of 2-amino-4-methylamino-6-chloro-5-methylthio pyrimidine, 48.3% of 4-amino-2-methylamino 6-chloro-5-methylthio pyrimidine and 1.4% 6-amino-4-methylamino-2 chloro-5-methylthio pyrimidine.
  • the synthesis is carried out in two stages.
  • the procedure is as in the first step of Example 1, using 18 g of ethylamine in 32.5% solution in water, 91.8 g of 2,4,4,6-trichloro-5-methylthio pyrimidine, 300 g of methyl ethyl ketone, 260 g of water and 16.2 g of sodium hydroxide.
  • the 2,4,4,6-butylthio-pyrimidine trichloro used as a starting product is prepared according to the process described in Example 6 for the preparation of the 2,4,4,6-ethylthio-pyrimidine trichloro, initially replacing the diethylsulfoxide with dibut-ylsulfoxide.
  • This compound is obtained according to the procedure of Example 1, replacing in the first stage the ethylamine by methylamine. It melts at 205 ° C and is characterized by its IR and NMR spectra.
  • EXAMPLE 11 Mixture of 4-methylamino-2 amino-6-chloro-5-methylthio-pyrimidine and 2-chloro-4-methylamino-6-amino-5-methylthio-pyrimidine.
  • This mixture is obtained according to the procedure of Example 5, replacing in the first stage the ethylamine with methylamine. It melts at 139 ° C and is characterized by its IR and NMR spectra.
  • This compound is obtained according to the procedure of Example 1, replacing in the 1st step the ethylamine with piperidine. It melts at 128 ° C and is characterized by its IR and NMR spectra.
  • This compound is obtained according to the oooutcire mode of Example 1, by replacing in the 1st stage the ethylamine with morpholine. It melts at 115 ° C and is characterized by its IR and NMR spectra.
  • the precipitate a (weight 6 g) consists essentially of the compound 4,6-dichloro-2 amino-5-methylthio pyrimidine.
  • Orecipity c (weight 17.2 g) consists of the compound 2,6-dichloro-4 amino-5-methylthio pyrimidine.
  • the isomers A and B are separated by preparative liquid chromatography from the mixture obtained in the 3rd step of Example 17.
  • the mixture is dissolved in chloroform supplemented with 2.5% ethanol and the solution is introduced at the head of a column 25 cm long and 22 mm inside diameter, filled with a silica gel of particle size 5 ⁇ known under the trade name LICHROSORB Si 60 (product sold by the company Merck). Eluted with chloroform supplemented with 2.5% ethanol. The fractions collected at the bottom of the column using a fraction collector are evaporated. 2.1 g of chloro-6 diamino-2,4 methylthio-5 pyrimidine, whose melting point is 171 ° C., and 0.9 g of chloro-2 diamino-4,6 methylthio-5 pyrimidine are thus obtained, whose melting point is 270 ° C.
  • EXAMPLE 19 the products according to the invention are formulated in the form of aqueous suspensions containing 5 ⁇ of an active-tension called "TWEEN 20".
  • the suspensions are applied by spraying either on 10-day-old plants, which makes it possible to study the post-emergence action of the products, or on seeds deposited on the soil surface, which makes it possible to study the action of pre-emergence. These seeds are covered with 2 cm of soil just after application.
  • the plants and seeds are placed in 18x12x5 cm plastic containers filled with standard soil made up of 3 parts of sand, 1 part of potting soil and 1 part of clay. After treatment, the containers are placed on an automatic irrigation tablet in a greenhouse maintained at 22 ° C and a humidity rate of 70
  • the plants tested are TRITICUM SP wheat, PHASEOLUS SP beans, BETA SP beet, SINAPIS SP mustard, TARAXACUM SP dandelion and ZEA SP corn.
  • Table No. I The results are collated in Table No. I.
  • the herbicidal efficacy of the compounds according to the invention with respect to the plants tested is expressed by a figure which represents the percentage of destruction of the plants in the treated batches. This percentage is evaluated by taking as a reference the plants from untreated control lots. The number 0 therefore indicates that the condition of the plants is the same in the treated lots and in the control lots, the number 100 that the plants are completely destroyed in the treated lots, which corresponds to maximum efficiency.
  • Tables II and III also show the results for a reference herbicide (chlortoluron).
  • the plants tested are TRITICUM SP wheat, ORDEUM SP barley, AVENA SP oats, ORYZA SP rice, GOSSYPIUM SP cotton, SETARIA SP foxtail, PANICUM SP panic, PASPALUM SP crabgrass and soybeans .
  • the compound according to the intention tested is that of Example 8.
  • Table IV The results obtained are collated in Table IV.
  • the meaning of the figures in Table IV is the same as that of the figures in Table I.
  • the number 0 indicates that the condition of the plants is the same in the treated lots and in the control lots, the figure 100 that the plants are entirely destroyed in the treated lots.
  • Example 8 The product of Example 8 is applied in the field, by spraying, on cultivated plants (wheat, zucchini, barley, broad beans, soybeans, sunflowers, rapeseed, corn, oats, peas, tomatoes) and unwanted weeds (chenopod , amaranth, nightshade, nightshade, milkweed, bindweed, senearme, foxtail), either in pre-emergence of the plants immediately after sowing, or in post-emergence of the plants 15 days after sowing.
  • the applied product doses are 2.5 or 5 kg / ha.
  • the note 100 therefore means that the vegetative energy of the plant is the same in the treated plots and in the control plots and the note 0 that the plant is entirely destroyed in the treated plots.
  • the note 0 means that the state of the plant is the same in the treated plots and the control plots and the note 100 that the plant is entirely destroyed in the treated plots.
  • Example 8 The product of Example 8 is applied by spraying on winter wheat crops of the Lutin variety, at different stages of the culture (pre-emergence, 3 leaves, tillering, end of tillering).
  • the applied product rates are 0.625 or 1.25 kg / ha.
  • Table VI are collected the results relating to the rate of destruction of weeds.
  • the note 0 corresponds to a free plant, the note 100 to a completely destroyed plant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Composés pyrimidiniques de formule:

Figure imga0001
dans laquelle RI est un groupe alkyle ayant 1 à 5 atomes de carbone, l'un des substituants X1, X2, X3 est un atome de chlore ou de brome, de préférence un atome de chlore, et les deux autres sont respectivement des groupes
Figure imga0002
dans lesquels R2 et R3 représentent, indépendamment l'un de l'autre, des atomes d'hydrogène ou des groupes alkyle de 1 à 5 atomes de carbone, cycloalkyle, aryle, aryle substitué ou
Figure imga0003
R étant un atome d'hydrogène ou un groupe alkyle de 1 à 5 atomes de carbone, ou forment ensembie avec l'atome d'azote auquel ils sont liés un radical hétérocyclique
Figure imga0004
autre que les radicaux pipérazino et pipérazino substitué, R4 ! et R, représentent, indépendamment l'un de
Figure imga0005
atomes d'hydrogène ou des groupes alkyle de
Figure imga0006
de carbone, cycloalkyle, aryle, aryle substitué ou
Figure imga0007
R étant tel que défini ci-dessus, ou forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique azoté autre que les radicaux pipérazino et pipérazine
Figure imga0008
tué, l'un au moins des groupes
Figure imga0009
étant un groupe NH2 ou
Figure imga0010
1 et leur sels avec les acides minéraux ou organiques,
Procédé de préparation des
Figure imga0011
(1). Ces composés sont des herbicides.Pyrimidine compounds of formula:
Figure imga0001
 in which R I is an alkyl group having 1 to 5 carbon atoms, one of the substituents X 1 , X 2 , X 3 is a chlorine or bromine atom, preferably a chlorine atom, and the other two are respectively groups
Figure imga0002
 in which R 2 and R 3 represent, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or
Figure imga0003
 R being a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, or together with the nitrogen atom to which they are attached form a heterocyclic radical
Figure imga0004
other than the piperazino and substituted piperazino radicals, R 4 ! and R, independently represent one of
Figure imga0005
hydrogen atoms or alkyl groups of
Figure imga0006
carbon, cycloalkyl, aryl, substituted aryl or
Figure imga0007
 R being as defined above, or together with the nitrogen atom to which they are linked form a heterocyclic nitrogen radical other than the piperazino and piperazine radicals
Figure imga0008
killed, at least one of the groups
Figure imga0009
 being an NH 2 group or
Figure imga0010
 1 and their salts with mineral or organic acids,
Process for the preparation of
Figure imga0011
(1). These compounds are herbicides.

Description

La présente invention a pour objet de nouvelles alkylthio-5 pyrimidines portant un groupe amino ou acylamino, leurs procédés de préparation et leur application en tant qu'herbicides.The present invention relates to novel 5-alkylthio-pyrimidines carrying an amino or acylamino group, their methods of preparation and their application as herbicides.

Il est déjà connu des dérivés de la pyrimidine herbicides (voir par exemple les brevets français 2.031.422, 2.317.291, 2.119.234, et 2.137.933), mais ces dérivés ne portent jamais simultanément un groupe alkylthio en position 5 et un groupe amino ou acylamino.Herbicide pyrimidine derivatives are already known (see for example French patents 2,031,422, 2,317,291, 2,119,234, and 2,137,933), but these derivatives never simultaneously carry an alkylthio group in position 5 and a amino or acylamino group.

Les nouvelles alkylthio-5 pyrimidinés selon l'invention peuvent être représentées par la formule générale :

Figure imgb0001
dans laquelle R1 est un groupe alkyle ayant 1 à 5 atomes de carbone, l'un des substituants X1, X2, X3 est un atome de chlore ou de brome, de préférence un atome de chlore, et les deux autres sont respectivement des groupes
Figure imgb0002
 dans lesquelsThe new 5-alkylthio pyrimidines according to the invention can be represented by the general formula:
Figure imgb0001
 in which R 1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X 1 , X 2 , X 3 is a chlorine or bromine atom, preferably a chlorine atom, and the other two are respectively groups
Figure imgb0002
 wherein

R2 et R3 représentent, indépendamment l'un de l'autre, des atomes d'hydrogène ou des groupes alkyle de 1 à 5 atomes de carbone, cycloalkyle, aryle, aryle substitué ou

Figure imgb0003
R étant un atome d'hydrogène ou un groupe alkyle de 1 à 5 atomes de carbone, ou forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique azoté autre que les radicaux pipérazino et pipérazino substitué, R4 et R5 représentent,indépendamment l'un de l'autre, des atomes d'hydrogène ou des groupes alkyle de 1 à 5 atomes de carbone, cycloalkyle, aryle, aryle substitué ou
Figure imgb0004
R étant tel que défini ci-dessus, ou forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique azoté autre que les radicaux pipérazino et pipérazino substitué, l'un au moins des groupes
Figure imgb0005
étant un groupe NH2 ou
Figure imgb0006
 R 2 and R 3 represent, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or
Figure imgb0003
 R being a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, or together with the nitrogen atom to which they are attached form a heterocyclic nitrogen radical other than the piperazino and substituted piperazino radicals, R 4 and R 5 represent, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or
Figure imgb0004
 R being as defined above, or together with the nitrogen atom to which they are linked form a heterocyclic nitrogen radical other than the piperazino and substituted piperazino radicals, at least one of the groups
Figure imgb0005
 being an NH 2 group or
Figure imgb0006

Dans les définitions données ci-dessus pour R2, R3, R4, R5, cycloalkyle est de préférence cyclohexyle et aryle est de préférence phényle. Comme exemples de radicaux hétérocycliques azotés on peut citer les radicaux pipéridino, morpholino et diméthyl-2,6 morpholino.In the definitions given above for R 2 , R 3 , R 4 , R 5 , cycloalkyl is preferably cyclohexyl and aryl is preferably phenyl. As examples of heterocyclic nitrogen radicals, mention may be made of the piperidino, morpholino and 2,6-dimethyl morpholino radicals.

Bien que la présente invention concerne les composés de formule (I) dans leur ensemble, elle a plus particulièrement pour objet ceux de ces composés pour lesquels X1 est un atome de chlore, l'un des substituants X2 et X3 est un groupe NH2

Figure imgb0007
et l'autre est un groupe NH2,
Figure imgb0008
 monoalkylamino ou dialkylamino dans lesquels les chaînes alkyle ont 1 à 5 atomes de carbone, pipéridino ou morpholino.Although the present invention relates to the compounds of formula (I) as a whole, it relates more particularly to those of these compounds for which X 1 is a chlorine atom, one of the substituents X 2 and X 3 is a group NH 2
Figure imgb0007
 and the other is an NH 2 group,
Figure imgb0008
 monoalkylamino or dialkylamino in which the alkyl chains have 1 to 5 carbon atoms, piperidino or morpholino.

Les composés de formule (I) dans lesquels R2, R3, R4, R5 ne sont pas

Figure imgb0009
et dans lesquels donc l'un au moins des groupes
Figure imgb0010
est un groupe NH2 peuvent être préparés par condensation d'une trihalo-2,4,6 alkylthio-5 pyrimidine de formule (II) avec un composé de formule (III) et condensation de la dihalo-4,6 (ou-2,6) alkylthio-5 pyrimidine de formule (IV) ou (IV) bis ainsi obtenue avec un composé de formule (V), suivant le schéma réactionnel :
Figure imgb0011
Figure imgb0012
 The compounds of formula (I) in which R 2 , R 3 , R 4 , R 5 are not
Figure imgb0009
 and in which therefore at least one of the groups
Figure imgb0010
 is an NH 2 group can be prepared by condensation of a 2,4,6-trihalo-5-alkylthio pyrimidine of formula (II) with a compound of formula (III) and condensation of 4,6-dihalo (or-2 , 6) 5-alkylthio pyrimidine of formula (IV) or (IV) bis thus obtained with a compound of formula (V), according to the reaction scheme:
Figure imgb0011
Figure imgb0012

Dans les formules (II) à (V), X est un atome atome de chlore ou de brome et R1, R2, R3, R4 et R ont les mêmes significations que dans la formule (I), excepté, pour R 2 à R 59 la signification

Figure imgb0013
L'un au moins des composés (III) et (V) est donc obligatoirement l'ammoniac, m et n sont des nombres supérieurs à 0 et inférieurs à 1.In formulas (II) to (V), X is a chlorine or bromine atom and R 1 , R 2 , R 3 , R 4 and R have the same meanings as in formula (I), except, for R 2 to R 59 meaning
Figure imgb0013
 At least one of the compounds (III) and (V) is therefore necessarily ammonia, m and n are numbers greater than 0 and less than 1.

Les tilhalo-2,4,6 alkylthio-5 pyrimidines de formule (II) sont des produits connus. Elles peuvept être préparées par exemple par le procédé décrit dans le brevet français 1.549.494 demandé le 31-octobre 1967.2,4,6-tilhalo-5,6-alkylthio pyrimidines of formula (II) are known products. They can be prepared for example by the process described in French patent 1,549,494 requested on October 31, 1967.

Les réactions de condensation (1), (2) et (2) bis peuvent être effectuées soit en milieu aqueux, soit en milieu solvant organique, soit encore dans un milieu mixte eau + solvant organique. Comme solvants organiques utilisables on peut citer en particulier, sans que cela soit limitatif, le toluène, le méthanol, des cétones aliphatiques comme l'acétone, la méthyléthylcétone ou la diéthylcétone, le diméthylformami- de ou un excès du composé (III) ou (V), lorsque celui-ci est une amine.The condensation reactions (1), (2) and (2) bis can be carried out either in an aqueous medium, or in an organic solvent medium, or even in a mixed water + organic solvent medium. As organic solvents which can be used, mention may in particular be made, without being limiting, of toluene, methanol, aliphatic ketones such as acetone, methyl ethyl ketone or diethyl ketone, dimethylformamide or an excess of compound (III) or ( V), when the latter is an amine.

Les réactions de condensation (1), (2) et (2) bis sont effectuées en présence d'un agent basique susceptible de fixer l'acide halohydrique HX formé dans la réaction. Comme agents basiques utilisables on peut citer, par exemple, les hydroxydes alcalins, l'ammoniaque, ou un excès des composés de formule (III) ou (V).The condensation reactions (1), (2) and (2) bis are carried out in the presence of a basic agent capable of fixing the hydrohalic acid HX formed in the reaction. As basic agents which can be used, there may be mentioned, for example, alkali metal hydroxides, ammonia, or an excess of the compounds of formula (III) or (V).

Les réactions (1), (2) et (2) bis sont effectuées à une température qui est fonction en particulier du solvant utilisé. De manière générale la réaction (1) est effectuée entre 0 et 150°C. Elle peut donc être réalisée à une température inférieure à la température ordinaire, par exemple entre 0 et 10°C, ou à une'température supérieure à la température ordinaire, par exemple entre 100 et 150°C. Les réactions (2) et (2) bis ne peuvent être réalisées à des températures aussi basses que celles utilisables pour la réaction (1). Elles sont effectuées en général entre 100 et 150°C. Selon la température et le solvant utilisés, les réactions (1), (2) et (2) bis sont effectuées à la pression atmosphérique ou sous une pression supérieure à la pression atmosphérique.Reactions (1), (2) and (2) bis are carried out at a temperature which depends in particular on the solvent used. In general, reaction (1) is carried out between 0 and 150 ° C. It can therefore be carried out at a temperature below the ordinary temperature, for example between 0 and 10 ° C, or at a temperature above the ordinary temperature, for example between 100 and 150 ° C. Reactions (2) and (2) bis cannot be carried out at temperatures as lower than those usable for the reaction (1). They are generally carried out between 100 and 150 ° C. Depending on the temperature and the solvent used, reactions (1), (2) and (2) bis are carried out at atmospheric pressure or under a pressure higher than atmospheric pressure.

Les dihalc alkylthio-5 pyrimidines isomères (IV) et (IV) bis obtenues dans la réaction (1) peuvent être séparées, par exemple par cristallisation fractionnée. Les isomères ainsi séparés fournissent ensuite, par les réactions (2) et (2) bis, le composé (I) pur et le mélange des deux composés isomères (I) bis et (I) ter.The ishalers (IV) and (IV) bis 5-alkylthio-pyrimidines dihalc obtained in reaction (1) can be separated, for example by fractional crystallization. The isomers thus separated then provide, by reactions (2) and (2) bis, the pure compound (I) and the mixture of the two isomeric compounds (I) bis and (I) ter.

On peut également soumettre le mélange des com- posés (IV) et (IV) bis obtenu dans la réaction (1) à la deuxième étape du procédé [réaction avec le composé (V)]. On obtient alors un mélange des trois composés isomères(I), (I) bis, et (I) ter, mélange qui peut être employé tel quel dans les applications herbicides. Les composés isomères (I), (I) bis et (I) ter peuvent aussi être séparés par chromatographie préparative en phase liquide.The mixture of compounds (IV) and (IV) bis obtained in reaction (1) can also be subjected to the second stage of the process [reaction with compound (V)]. A mixture of the three isomeric compounds (I), (I) bis, and (I) ter is then obtained, a mixture which can be used as it is in herbicidal applications. The isomeric compounds (I), (I) bis and (I) ter can also be separated by preparative liquid chromatography.

Dans le cas où les composés (III) et (V) sont identiques et sont donc tous les deux l'ammoniac, les isomères (I) et (I) bis sont identiques et l'ensemble du schéma réactionnel précédent conduit donc à deux isomères [isomères de formules (VI) et (VII) ci-dessous]. Dans ce même cas, et à condition d'opérer à température suffisamment élevée (100 à 150°C dans la pratique), on peut obtenir en une seule étape,à partir de la trihalo-2,4,6 alkylthio-5 pyrimidine de formule (II), un mélange des isomères (VI) et (VII), suivant la réaction:;

Figure imgb0014
In the case where the compounds (III) and (V) are identical and are therefore both ammonia, the isomers (I) and (I) bis are identical and the whole of the preceding reaction scheme therefore leads to two isomers [isomers of formulas (VI) and (VII) below]. In the same case, and provided that the operation is carried out at a sufficiently high temperature (100 to 150 ° C. in practice), it is possible to obtain, in a single step, from 2,4,4,6-trihalo-5-alkylthio-pyrimidine. formula (II), a mixture of the isomers (VI) and (VII), according to the reaction :;
Figure imgb0014

Dans ce mélange l'isomère (VI) est prépondérant (a inférieur à 1 et supérieur à 0,5).In this mixture the isomer (VI) is predominant (a less than 1 and greater than 0.5).

Les composés de formule (I) dans lesquels X1 est un atome de chlore ou de brome, X3 est un groupe NH2 et X2 est un groupe

Figure imgb0015
dans lequel R2 et R3 sont des groupes alkyle identiques R' peuvent aussi être préparés par réaction d'une trihalo-2,4,6 alkylthio-5 pyrimidine de formule (II) avec une amine tertiaire de formule (VIII) et condensation de la dihalo-4,6 alkylthio-5 pyrimidine de formule (IX) ainsi obtenue avec l'ammoniac, suivant le schéma réactionnel suivant :
Figure imgb0016
Figure imgb0017
 The compounds of formula (I) in which X 1 is a chlorine or bromine atom, X 3 is an NH 2 group and X 2 is a group
Figure imgb0015
 in which R 2 and R 3 are identical alkyl groups R 'can also be prepared by reaction of a 2,4,6-trihalo-5-alkylthio pyrimidine of formula (II) with a tertiary amine of formula (VIII) and condensation 4,6-dihalo-5-alkylthio pyrimidine of formula (IX) thus obtained with ammonia, according to the following reaction scheme:
Figure imgb0016
Figure imgb0017

La réaction (4), qui présente l'originalité de fournir sélectivement l'isomère dihalo-4,6 alkylthio-5 pyrimidine, peut être effectuée en milieu solvant organique, à une température comprise entre 100 et 150"C. Comme solvants organiques utilisables on peut citer les mêmes solvants que pour les réactions (1), (2) et (2) bis.Reaction (4), which has the originality of selectively providing the 4,6-dihalo-5-alkylthio-pyrimidine isomer, can be carried out in an organic solvent medium, at a temperature between 100 and 150 "C. As usable organic solvents the same solvents can be mentioned as for reactions (1), (2) and (2) bis.

La réaction (5) est réalisée dans les mêmes conditions que la réaction (2).Reaction (5) is carried out under the same conditions as reaction (2).

Les composés formés dans les réactions (1), (2),(2) bis,(3), (4) et (5) peuvent être isolés du milieu réactionnel par des méthodes classiques telles que, par exemple, la filtration, lorsque les composés précipitent, ou la distillation sous pression réduite du solvant suivie du lavage à l'eau du résidu, et purifiés par recristallisation dans un solvant approprié.The compounds formed in reactions (1), (2), (2) bis, (3), (4) and (5) can be isolated from the reaction medium by conventional methods such as, for example, filtration, when the compounds precipitate, or the distillation under reduced pressure of the solvent followed by washing the residue with water, and purified by recrystallization from an appropriate solvent.

Les composés de formule (I) dans lesquels l'un au moins des substituants R2, R3, R4, R5 est un groupe

Figure imgb0018
peuvent être préparés par acylation des composés de formule (I) dans lesquels R2, R3, R4, R5 ne sont pas
Figure imgb0019
Cette acylation est effectuée à l'aide des agents d'acylation habituels tels que chlorures d'acide, anhydrides d'acide, cétène ou composés homologues. On opère en milieu solvant organique, à une température comprise entre 20 et 120°C, de préférence entre 50 et 100°C. Comme solvants organiques utilisables on peut citer en particulier les acides carboxyliques, dans le cas où on effectue l'acylation avec un anhydride d'acide, et la pyridine, dans le cas où on effectue l'acylation avec un chlorure d'acide.The compounds of formula (I) in which at least one of the substituents R 2 , R 3 , R 4 , R 5 is a group
Figure imgb0018
 can be prepared by acylation of the compounds of formula (I) in which R 2 , R 3 , R 4 , R 5 are not
Figure imgb0019
 This acylation is carried out using the usual acylating agents such as acid chlorides, acid anhydrides, ketene or homologous compounds. The operation is carried out in an organic solvent medium, at a temperature between 20 and 120 ° C., preferably between 50 and 100 ° C. As organic solvents which can be used, mention may in particular be made of carboxylic acids, in the case where the acylation is carried out with an acid anhydride, and pyridine, in the case where the acylation is carried out with an acid chloride.

Les composés de formule (I) peuvent être transformés en leurs sels avec les acides minéraux ou organiques par réaction avec l'acide correspondant au sein d'un solvant approprié.The compounds of formula (I) can be transformed into their salts with mineral or organic acids by reaction with the corresponding acid in an appropriate solvent.

Les composés de formule (I) et leurs sels avec les acides minéraux ou organiques ont La propriété de détruire un grand nombre de plantes indésirables appartenant aux classes des monocotylédones ou des dicotylédones et ce à des doses très faibles comprises entre 150 g/ha et 2500 g/ha. En particulier ils détruisent totalement les plantes suivantes : ray grass, panic, digitaire, sétaire, vulpin, folle avoine, gaillet, amarante, renouée, capselle, véronique, moutarde, datura, mouron, stellaire, chardon, fumeterre, chenopode, oseille, plantain, atriclex, pissenlit, coquelicot, chrysanthème, seneçon, laiteron, euphorbe. En outre, aux doses auxquelles ils sont actifs vis-à-vis des plantes indésirables, les composés de formule (I) et leurs sels n'ont en général pas d'action défavorable sur des céréales d'hiver et de printemps telles que le blé et l'orge, sur le riz et le mais.The compounds of formula (I) and their salts with mineral or organic acids have the property of destroying a large number of undesirable plants belonging to the classes of monocots or dicots and this at very low doses of between 150 g / ha and 2500 g / ha. In particular, they totally destroy the following plants: ryegrass, switchgrass, crabgrass, foxtail, wild oats, bedstraw, amaranth, knotweed, capsella, speedwell, mustard, datura, chickweed, stellar, thistle, fumitory, chenopoda, sorrel, plantain , atriclex, dandelion, poppy, chrysanthemum, seneçon, milkweed, spurge. In addition, at the doses at which they are active against undesirable plants, the compounds of formula (I) and their salts generally have no unfavorable action on winter and spring cereals such as wheat and barley, on rice and corn.

Les composés de formule (I) et leurs sels sont actifs vis-à-vis des plantes adventices aussi bien dans les traitements de pré-levée que dans les traitements de post-levée. Toutefois leur activité est plus marquée dans les traitements de post-levée.The compounds of formula (I) and their salts are active with regard to weeds as well in pre-emergence treatments as in post-emergence treatments. However, their activity is more marked in post-emergence treatments.

Pour leur mise en oeuvre les composés herbicides selon l'invention peuvent être incorporés, conjointement avec d'autres herbicides ou séparément, dans des formulations qui contiennent, outre la matière active, les additifs inertes habituellement utilisés en agriculture pour faciliter la conservation, la mise en suspension aqueuse, l'adhérence sur le feuillage et la résistance aux agents atmosphériques et aux dégradations biologiques (d'où une persistance plus grande de l'action), tels que diluants solides (talc, silice, kieselguhr, argile, etc...) ou liquides (huiles minérales, eau, solvants organiques comme par exemple des cétones, des alcools, des hydrocarbures ou leurs dérivés chlorés), adjuvants, tensio actifs, antioxydants et stabilisants. De telles formulations peuvent se présenter sous la forme de poudres mouillables, solutions émulsifiables dans l'eau, suspensions, granulés ou toute autre forme en usage dans le domaine des herbicides.For their implementation, the herbicidal compounds according to the invention can be incorporated, jointly with other herbicides or separately, in formulations which contain, in addition to the active material, the inert additives usually used in agriculture to facilitate the preservation, in aqueous suspension, adhesion to the foliage and resistance to atmospheric agents and biological degradation (hence greater persistence of the action), such as solid diluents (talc, silica, kieselguhr, clay, etc.) .) or liquids (mineral oils, water, organic solvents such as ketones, alcohols, hydrocarbons or their chlorinated derivatives), adjuvants, surfactants, antioxidants and stabilizers. Such formulations can be in the form of wettable powders, solutions emulsifiable in water, suspensions, granules or any other form in use in the field of herbicides.

Dans les formulations contenant seulement des composés herbicides selon l'invention et des additifs inertes, la teneur en composes de formule (I) ou leurs sels (matière active) peut varier de 1 % à 95 % en poids. Dans les formulations contenant des composés herbicides selon l'invention, d'autres herbicides et des additifs inertes, la teneur en composés selon l'invention peut varier de 1 % à 80 % en poids, celle en herbicides autres de 80 % à 1 % en poids, le complément à 100 étant constitué par les additifs inertes.In formulations containing only herbicidal compounds according to the invention and inert additives, the content of compounds of formula (I) or their salts (active material) can vary from 1% to 95% by weight. In the formulations containing herbicidal compounds according to the invention, other herbicides and inert additives, the content of compounds according to the invention can vary from 1% to 80% by weight, that in other herbicides from 80% to 1% by weight, the complement to 100 being constituted by inert additives.

Comme herbicides autres qui peuvent être associés dans les formulations aux composés selon l'invention on peut citer la (dichloro-3,4 phényl)-3 diméthyl-1,1 urée (diuron), la phényl-3 diméthyl-1,1 urée (fénuron), la (chloro-3 méthyl-4 phényl )-3 diméthyl-1,1 urée (chlortoluron), la (chloro-4 phényl)-3 diméthyl-1,1 urée (monuron), le monolinuron, la (dichloro-3,4 phényl)-3 méthoxy-1 méthyl-1 urée (linuron), l'isoproturon, le mithabenzthiazuron, la (dichloro-3,4 phényl)-3 n-butyl-1 méthyl-1 urée (néburon), la chloro-2 éthylamino-4 isopropylamino-6 triazine-1,3,5 (atrazine), la chloro-2 bis (éthylamino)-4,6 triazine-1,3,5 (simazine), l'amino-3 triazole-1,2,4, la terbutryne, la cyanazine, la diéthyl-2,6 N-chloroacétyl N-méthoxyméthyl aniline (alachlor), la N-chloroacétyl N-iso- propyl aniline (propachlor), le napropamide, le diquat, le paraquat, l'acide dichloro-2,4 phénoxyacétique (2,4-D), l'acide (méthyl-2 chloro-4 phénoxy)-2 propionique (MCPP), l'acide méthoxy-2 dichloro-3,6 benzoïque (dicamba), l'acide amino-4 trichloro-3,5,6 picolinique (picloram), le dinitro-2,4 sec-butyl-6 phénol (dinoseb), le dinitro-4,6 ortho-crésol (DNOC), le N-(chloro-3 phényl) carbamate de chloro-4 butynyle-2 (barban), le propham, le terbacile, le bromo-5 sec-butyl-3 méthyl-6 uracile (bromacile), le pyrazone, le phenmedipham et le métamitron.As other herbicides which can be combined in the formulations with the compounds according to the invention, mention may be made of (3,4-dichloro-phenyl) -3-dimethyl-1,1 urea (diuron), 3-phenyl-dimethyl-1,1 urea (fenuron), (3-chloro-4-methylphenyl) -3 dimethyl-1,1 urea (chlortoluron), ((chloro-4 phenyl) -3 dimethyl-1,1 urea (monuron), monolinuron, ( dichloro-3,4-phenyl) -3 methoxy-1 methyl-1 urea (linuron), isoproturon, mithabenzthiazuron, (dichloro-3,4 phenyl) -3 n-butyl-1 methyl-1 urea (neburon) , 2-chloro-ethylamino-4 isopropylamino-6 triazine-1,3,5 (atrazine), chloro-2 bis (ethylamino) -4,6 triazine-1,3,5 (simazine), amino-3 triazole-1,2,4, terbutryne, cyanazine, 2,6-diethyl N-chloroacetyl N-methoxymethyl aniline (alachlor), N-chloroacetyl N-isopropyl aniline (propachlor), napropamide, diquat , paraquat, 2,4-dichloro-phenoxyacetic acid (2,4-D), (2-methyl-4-chloro-phenoxy) -2 propionic acid (MCPP), 2-methoxy-3-dichloro-acid, 6 benzoic ( dicamba), 4-amino-3,5,6-trichloro-picolinic acid (picloram), 2,4-dinitro-6-sec-butyl-phenol (dinoseb), 4,6-dinitro ortho-cresol (DNOC), N-(3-chloro-phenyl) 4-chloro-2-butynyl carbamate (barban), propham, terbacil, bromo-5 sec-butyl-3 methyl-6 uracil (bromacile), pyrazone, phenmedipham and the metamitron.

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

EXEMPLE 1 Amino-4 chloro-6 éthylamino-2 méthylthio-5 pyrimidine.EXAMPLE 1 Amino-4 chloro-6 ethylamino-2 methylthio-5 pyrimidine.

La préparation de ce composé est réalisée en 2 étapes.The preparation of this compound is carried out in 2 stages.

1ère étape :1st step :

Dans un réacteur de 250 ml muni d'une agitation, on introduit 45,9 g de trichloro-2,4,6 méthylthio-5 pyrimidine, 150 g de méthyléthylcétone et 130 g d'eau. Dans ce mélange maintenu à 5°C, on ajoute en 30 minutes 9,44 g d'éthylamine en solution aqueuse à 32,5 %. On maintient 1 h 30 à 5°C. On ajoute ensuite 8,08 g de soude en solution aqueuse à 30 %. On maintient le mélange 4 heures à 20°C et une nuit au réfrigérateur à environ 0°C. Il apparait un précipité qui est isolé par filtration, lavé avec 16 ml de méthyléthylcétone et recristallisé deux fois dans 180 ml d'éthanol. On obtient ainsi 10,5 g d'éthylamino-2 dichloro-4,6 méthylthio-5 pyrimidine, qui fond à 147°C et qui est identifiée par son spectre dans l'infrarouge (IR) et son spectre de résonance magnétique nucléaire (RMN).45.9 g of 2,4,6-trichloro-5-methylthio pyrimidine, 150 g of methyl ethyl ketone and 130 g of water are introduced into a 250 ml reactor fitted with stirring. 9.44 g of ethylamine in 32.5% aqueous solution are added to this mixture maintained at 5 ° C. over 30 minutes. It is maintained for 1 hour 30 minutes at 5 ° C. We add then 8.08 g of sodium hydroxide in 30% aqueous solution. The mixture is kept for 4 hours at 20 ° C. and overnight in the refrigerator at approximately 0 ° C. A precipitate appears which is isolated by filtration, washed with 16 ml of methyl ethyl ketone and recrystallized twice from 180 ml of ethanol. This gives 10.5 g of 2-ethylamino-4,6-dichloro-5-methylthio pyrimidine, which melts at 147 ° C. and which is identified by its infrared spectrum (IR) and its nuclear magnetic resonance spectrum ( NMR).

Le filtrat est évaporé. On obtient ainsi 36,5 g d'un mélange d'éthylamino-2 dichloro-4,6 méthylthio-5 pyrimidine et d'éthylamino-4 dichloro-2,6 méthylthio-5 pyrimidine, mélange qui fond à 76°C et qui est identifié par ses spectres IR et RMN.The filtrate is evaporated. 36.5 g of a mixture of 2-ethylamino-4,6-dichloro-5-methylthio-pyrimidine and of 4-ethylamino-2,6-dichloro-5-methylthio-5-pyrimidine are thus obtained, a mixture which melts at 76 ° C. is identified by its IR and NMR spectra.

2ème étape :2nd step:

Dans un autoclave de 500 ml, on introduit 7,5 g d'éthylamino-2 dichloro-4,6 méthylthio-5 pyrimidine obtenue comme indiqué ci-dessus, 110 ml de méthanol et 11 g d'ammoniac. Le mélange est chauffé à 110°C pendant 2 heures puis refroidi. On concentre sous pression réduite la solution obtenue et lave à l'eau le résidu. On obtient ainsi 8,2 g d'amino-4 chloro-6 éthylamino-2 méthylthio-5 pyrimidine, qui est identifiée par ses spectres IR et RMN et qui fond à 124°C.7.5 g of 2-ethylamino-4,6-dichloro-5-methylthio-pyrimidine obtained as indicated above, 110 ml of methanol and 11 g of ammonia are introduced into a 500 ml autoclave. The mixture is heated at 110 ° C for 2 hours and then cooled. The solution obtained is concentrated under reduced pressure and the residue is washed with water. 8.2 g of 4-amino-6-chloro-2-ethylamino-5-methylthio-pyrimidine are thus obtained, which is identified by its IR and NMR spectra and which melts at 124 ° C.

EXEMPLE 2 Mélange des trois isomères amino-4 chloro-6 éthylamino-2 méthylthio-5 pyrimidine, amino-2 chloro-6 éthylamino-4 méthylthio-5 pyrimidine et chloro-2 amino-6 éthylamino-4 méthylthio-5 pyrimidine.EXAMPLE 2 Mixture of the three isomers of 4-amino-6-chloro-2-ethylamino-5-methylthio pyrimidine, 2-amino-6-chloro-4-ethylamino-5-methylthio-pyrimidine and 2-chloro-6 amino-4-ethylamino-5-pyrimidine.

Dans un autoclave de 500 ml, on introduit 2,5 g d'éthylamino-2 dichloro-4,6 méthylthio-5 pyrimidine, 9'g du mélange d'éthylamino-2 dichloro-4,6 méthylthio-5 pyrimidine et d'éthylamino-4 dichloro-2,6 méthylthio-5 pyrimidine obtenu à la première étape de l'exemple 1, 165 g de méthanol et 16 g d'ammoniac. Le mélange est chauffé 2 heures à 120°C puis refroidi. On concentre sous pression réduite la solution obtenue et lave à l'eau le résidu. On obtient ainsi 8,2 g d'un mélange fondant à 76°C. L'analyse de ce mélange par chromatographie en phase gazeuse et spectrométrie de masse montre qu'il contient 56,6 % d'amino-2 chloro-6 éthylamino-4 méthylthio-5 pyrimidine, 37,8 % d'amino-4 éthylamino-2 chloro-6 méthylthio-5 pyrimidine et 5,6 % d'amino-6 éthylamino-4 chloro-2 méthylthio-5 pyrimidine.2.5 g of 2-ethylamino-4,6-dichloro-5-methylthio pyrimidine, 9 g of the mixture of 2-ethylamino-4-dichloro-4,6-methylthio-5 pyrimidine and 4,6-ethylamino-2,6-dichloro-5-methylthio pyrimidine obtained in the first step of Example 1, 165 g of methanol and 16 g of ammonia. The mixture is heated for 2 hours at 120 ° C. and then cooled. The solution obtained is concentrated under reduced pressure and the residue is washed with water. 8.2 g of a mixture are thus obtained melting at 76 ° C. Analysis of this mixture by gas chromatography and mass spectrometry shows that it contains 56.6% 2-amino-6 chloro-4 ethylamino-5 methylthio pyrimidine, 37.8% amino-4 ethylamino -2 chloro-6 methylthio-5 pyrimidine and 5.6% amino-6 ethylamino-4 chloro-2 methylthio-5 pyrimidine.

EXEMPLE - 3 - Mélange des trois isomères amino-2 chloro-6 isopropylamino-4 méthylthio-5 pyrimidine, amino-4 chloro-6 isopropylamino-2 méthylthio-5 pyrimidine et amino-6 isopropylamino-4 chloro-2 méthylthio-5 pyrimidine.EXAMPLE 3 Mixture of the three isomers of 2-amino-6-chloro-4-isopropylamino-5-methylthio pyrimidine, 4-amino-6-chloro-isopropylamino-2-methylthio-5 pyrimidine and 6-amino isopropylamino-4 chloro-2 methylthio-5 pyrimidine.

La synthèse est réalisée en 2 étapes.The synthesis is carried out in 2 steps.

1ère étape :1st step :

On opère comme dans la première étape de l'exemple 1 en remplaçant l'éthylamine par 11,B g d'isopropylamine, Par évaporation sous pression réduite de la solution finale, lavage à l'eau du résidu et séchage sous pression réduite, on obtient 51,4 g d'une pâte constituée par un mélange de dichloro-4,6 isopropylamino-2 méthylthio-5 pyrimidine et de dichloro-2,6 isopropylamino-4 méthylthio-5 pyrimidine.The procedure is as in the first step of Example 1, replacing the ethylamine with 11.5 B of isopropylamine. By evaporation of the final solution under reduced pressure, washing the residue with water and drying under reduced pressure, obtains 51.4 g of a paste consisting of a mixture of 4,6-dichloro-2-isopropylamino-5-methylthio-pyrimidine and 2,6-dichloro-4-isopropylamino-4-methylthio-5-pyrimidine.

2ème étape :2nd step:

Dans un autoclave de 500 ml, on introduit 12,5 g du mélange obtenu à la première étape, 250 g de méthanol et 25 g d'ammoniac. Après 2 heures de chauffage à 130°C, on concentre sous vide la solution obtenue et lave à l'eau le résidu. On obtient ainsi 12,1 g d'un produit pâteux qui, ainsi que le montrent la chromatographie en phase gazeuse et la spectrométrie de masse, est un mélange contenant 55,1 % d'amino-2 chloro-6 isopropylamino-4 méthylthio-5 pyrimidine, 39,4 % d'amino-4 chloro-6 isopropylamino-2 méthylthio-5 pyrimidine et 5,5 % d'isopropylamino-4 amino-6 chloro-2 méthylthio-5 pyrimidine..12.5 g of the mixture obtained in the first step, 250 g of methanol and 25 g of ammonia are introduced into a 500 ml autoclave. After 2 hours of heating to 130 ° C., the solution obtained is concentrated under vacuum and the residue is washed with water. 12.1 g of a pasty product are thus obtained which, as shown by gas chromatography and mass spectrometry, is a mixture containing 55.1% 2-amino-6-chloro-4-isopropylamino-methylthio- 5 pyrimidine, 39.4% 4-amino-6-chloro-2-isopropylamino-5-methylthio pyrimidine and 5.5% 4-isopropylamino-6-amino 2-chloro-5-methylthio-pyrimidine.

EXEMPLE 4 - Mélange des trois isomères amino-2 chloro-6 méthylamino-4 méthylthio-5 pyrimidine, amino-4 chloro-6 méthylamino-2 méthylthio-5 pyrimidine et amino-6 chloro-2 méthylamino-4 méthylthio-5 pyrimidine.EXAMPLE 4 Mixture of the three isomers of 2-amino-6-chloro-4-methylamino-5-methylthio-pyrimidine, 4-amino-6-chloro-6-methylamino-2-methylthio-5 pyrimidine and 6-amino-2-chloro-4-methylamino-pyrimidine.

La synthèse est réalisée en deux étapes.The synthesis is carried out in two stages.

1ère étape :1st step :

On opère comme dans la première étape de l'exemple 1 en remplaçant l'éthylamine par 6,2 g de méthylamine en solution à 30,7 % dans l'eau. Après réaction, on obtient par filtration 13 g d'un précipité constitué de dichloro-4,6 méthylamino-2 méthylthio-5 pyrimidine de point de fusion 142°C.The procedure is as in the first step of Example 1, replacing the ethylamine with 6.2 g of methylamine in solution at 30.7% in water. After reaction, 13 g of a precipitate consisting of 4,6-dichloro-2-methylamino-5-methylthio-pyrimidine with a melting point of 142 ° C. are obtained by filtration.

Par concentration sous oression réduite du filtrat et lavage à l'eau du résidu, on obtient 33,4 g d'un produit fondant à 91°C qui, ainsi que le montrent les spectres IR et RMN, est un mélange de dichloro-4,6 méthylamino-2 méthylthio-5 pyrimidine et de dichloro-2,6 méthylamino-4 méthylthio-5 pyrimidine.By concentration under reduced oression of the filtrate and washing with water of the residue, 33.4 g of a product melting at 91 ° C. are obtained which, as the IR and NMR spectra show, is a mixture of 4-dichloro , 6 methylamino-2 methylthio-5 pyrimidine and dichloro-2,6 methylamino-4 methylthio-5 pyrimidine.

2ème étape2nd stage

Dans un autoclave de 500 ml, on introduit 6 g de dichloro-4,6 méthylamino-2 méthylthio-5 pyrimidine, 20,6 g du mélange des deux isomères obtenu à la lère étape, 50 g d'ammoniac et 350 g de méthanol. Après deux heures de chauffage à 130°C, on concentre sous vide la solution obtenue et lave à l'eau le résidu. On obtient ainsi 20,6 g d'un mélange, fondant à 118°C. Comme le montrent la chromatographie en phase gazeuse et la spectrométrie de masse, ce mélange contient 50,3 d'amino-2 méthyl-amino-4 chloro-6 méthylthio-5 pyrimidine, 48, 3 % d'amino-4 méthylamino-2 chloro-6 méthylthio-5 pyrimidine et 1,4 % d'amino-6 méthylamino-4 chloro-2 méthylthio-5 pyrimidine.6 g of 4,6-dichloro-2-methylamino-5-methylthio-pyrimidine, 20.6 g of the mixture of the two isomers obtained in the 1st step, 50 g of ammonia and 350 g of methanol are introduced into a 500 ml autoclave . After two hours of heating at 130 ° C., the solution obtained is concentrated under vacuum and the residue is washed with water. 20.6 g of a mixture are thus obtained, melting at 118 ° C. As shown by gas chromatography and mass spectrometry, this mixture contains 50.3 of 2-amino-4-methylamino-6-chloro-5-methylthio pyrimidine, 48.3% of 4-amino-2-methylamino 6-chloro-5-methylthio pyrimidine and 1.4% 6-amino-4-methylamino-2 chloro-5-methylthio pyrimidine.

EXEMPLE 5 - Mélange d'amino-2 chloro-6 éthylamino-4 méthylthio-5 pyrimidine et amino-6 chloro-2 éthylamino-4 méthylthio-5 pyrimidine.EXAMPLE 5 Mixture of 2-amino-6-chloro-4-ethylamino-5-methylthio pyrimidine and 6-amino 2-chloro-4-ethylamino-5-methylthio-pyrimidine.

La synthèse est réalisée en deux étapes.The synthesis is carried out in two stages.

1ère étape:1st step:

On opère comme dans la première étape de l'exemple 1 en utilisant 18 g d'éthylamine en solution à 32,5 % dans l'eau, 91,8 g de trichloro-2,4,6 méthylthio-5 pyrimidine, 300 g de méthyléthylcétone, 260 g d'eau et 16,2 g de soude.The procedure is as in the first step of Example 1, using 18 g of ethylamine in 32.5% solution in water, 91.8 g of 2,4,4,6-trichloro-5-methylthio pyrimidine, 300 g of methyl ethyl ketone, 260 g of water and 16.2 g of sodium hydroxide.

En fin de réaction, on recueille par filtration 25,5 g de dichloro-4,6 éthylamino-2 méthylthio-5 pyrimidine.At the end of the reaction, 25.5 g of 4,6-dichloro-2-ethylamino-5-methylthio-pyrimidine are collected by filtration.

Le filtrat est concentré sous pression réduite et le résidu obtenu est dissous dans 280 ml d'acide chlorhydrique concontré. A la solution obtenue on ajoute 112 ml d'eau. On recueille alors par filtration 11,5 g d'un mélange de dichloro-4,6 éthylamino-2 méthylthio-5 pyrimidine et de dichloro-2,6 éthylamino-4 méthylthio-5 pyrimidine. Au filtrat on ajoute encore 2 litres d'eau. Par une nouvelle filtration, on recueille 36 g de dichloro-2,6 éthylamino-4 méthylthio-5 pyrimidine de point de fusion 80°C.The filtrate is concentrated under reduced pressure and the residue obtained is dissolved in 280 ml of concentrated hydrochloric acid. To the solution obtained is added 112 ml of water. 11.5 g of a mixture of 4,6-dichloro-2-ethylamino-5-methylthio-pyrimidine and 2,6-dichloro-4-ethylamino-5-methylthio-5-pyrimidine are then collected by filtration. To the filtrate another 2 liters of water are added. By a new filtration, 36 g of 2,6-dichloro-4-ethylamino-5-methylthio-pyrimidine with a melting point of 80 ° C. are collected.

2ème étape2nd stage

Dans un autoclave de 500 ml, on introduit 18 g de dichloro-2,6 éthylamino-4 méthylthio-5 pyrimidine,220 ml de méthanol et 40 g d'ammoniac. Après 2 heures de chauffage à 130°C, on évapore la solution sous pression réduite. Par recristallisation du résidu dans un mélange éthanol-eau, on recueille 10,8 g d'un mélange fondant à 100°C. Comme le montrent la chromatographie en phase gazeuse et la spectrométrie de masse, ce mélange contient 94,4 % d'amino-2 éthylamino-4 chloro-6 méthylthio-5 pyrimidine et 5,6 % d'amino-6 éthylamino-4 chloro-2 méthylthio-5 pyrimidine.18 g of 2,6-dichloro-4 ethylamino-5-methylthio-pyrimidine, 220 ml of methanol and 40 g of ammonia are introduced into a 500 ml autoclave. After 2 hours of heating to 130 ° C., the solution is evaporated under reduced pressure. By recrystallization of the residue from an ethanol-water mixture, 10.8 g of a mixture melting at 100 ° C. are collected. As shown by gas chromatography and mass spectrometry, this mixture contains 94.4% 2-amino-4-ethylamino-6 chloro-5-methylthio pyrimidine and 5.6% 6-amino-4 ethylamino-chloro -2 5-methylthio pyrimidine.

/EXEMPLE 6/ - Chloro-6 diamino-2,4 éthylthio-5 pyrimidine./ EXAMPLE 6 / - Chloro-6 diamino-2,4-ethylthio-5 pyrimidine.

On chauffa à 95 °C pendent 5 h 30 un mélange de 24,6 g d'acide barbiturique, 20 g de diéthylsulfoxyde, 75 ml d'acide acétique glacial et 28 ml d'anhydride acétique. Après refroidissement, on ajoute à froid 175 ml d'eau. Le précipité obtenu est filtré, lavé à l'acétone et séché sous pression réduite. On obtient ainsi 21,7 g de diéthylsulfonium-5 barbiturylide.A mixture of 24.6 g of barbituric acid, 20 g of diethyl sulfoxide, 75 ml of glacial acetic acid and 28 ml of acetic anhydride was heated to 95 ° C. for 5 h 30 min. After cooling, 175 ml of water are added cold. The precipitate obtained is filtered, washed with acetone and dried under reduced pressure. 21.7 g of 5-diethylsulfonium barbiturylide are thus obtained.

Aux 21,7 g de diéthylsulfonium-5 barbiturylide on ajoute 84,4 g d'oxychlorure de phosphore, 5 ml de diméthy- laniline et on chauffe le mélange obtenu à l'ébullition pendant 20 heures. Après refroidissement à 60°C, on coule le mélange réactionnel sur de la glace et on agite 1 heure. On filtre le précipité obtenu, on le sèche et on le recristallise dans l'hexane. On obtient ainsi 10 g de trichloro-2,4,6 éthylthio-5 pyrimidine de point de fusion 62-64°C.To the 21.7 g of 5-diethylsulfonium barbiturylide are added 84.4 g of phosphorus oxychloride, 5 ml of dimethylaniline and the mixture obtained is heated to boiling for 20 hours. After cooling to 60 ° C., the reaction mixture is poured onto ice and stirred for 1 hour. We filter the precipitate obtained is dried and recrystallized from hexane. 10 g of trichloro-2,4,6-ethylthio-pyrimidine with a melting point of 62-64 ° C. are thus obtained.

Dans un autoclave de 500 ml, on introduit 10 g de trichloro-2,4,6 éthylthio-5 pyrimidine, 17 g d'ammoniac et 100 g de méthanol. Après 2 heures de réaction à 100°C, on filtre le précipité obtenu, on le lave à l'eau et on le sèche sous pression réduite. On obtient ainsi 5,6 g d'un produit fondant à 182°C et consistant essentiellement en chloro-6 diamino-2,4 éthylthio-5 pyrimidine. Ce produit. est caractérisé par ses spectres IR, RMN et de masse.10 g of 2,4,4,6-trichloro-ethylthio pyrimidine, 17 g of ammonia and 100 g of methanol are introduced into a 500 ml autoclave. After 2 hours of reaction at 100 ° C., the precipitate obtained is filtered, washed with water and dried under reduced pressure. This gives 5.6 g of a product melting at 182 ° C and consisting essentially of 6-chloro-2,4-diamino-5-ethylthio-pyrimidine. This product. is characterized by its IR, NMR and mass spectra.

EXEMPLE 7/- Chloro-6 diamino-2,4 butylthio-5 pyrimidine.EXAMPLE 7 / Chloro-6 diamino-2,4 butylthio-5 pyrimidine.

Dans un autoclave de 500 ml, on chauffe à 100°C, pendant 2 heures, 120 g de méthanol, 20 g d'ammoniac et 17 g de trichloro-2,4,6 butylthio-5 pyrimidine. Après refroidissement, la solution obtenue est concentrée sous pression réduite. On lave à l'eau le résidu obtenu , et on le recristallise dans le propanol. On obtient ainsi 7 g d'un produit fondant à 129°C et consistant essentiellement en chloro-6 diamino-2,4 butylthio-5 pyrimidine. Ce produit est caractérisé par ses spectres IR, RMN et de masse.120 g of methanol, 20 g of ammonia and 17 g of 2,4,4,6-butylthio-pyrimidine are heated at 100 ° C. for 2 hours in a 500 ml autoclave. After cooling, the solution obtained is concentrated under reduced pressure. The residue obtained is washed with water and recrystallized from propanol. 7 g of a product are thus obtained, melting at 129 ° C. and consisting essentially of 6-chloro-2,4-diamino-5-butylthio-pyrimidine. This product is characterized by its IR, NMR and mass spectra.

La trichloro-2,4,6 butylthio-5 pyrimidine utilisée comme produit de départ est préparée selon le procédé décrit à l'exemple 6 pour la préparation de la trichloro-2,4,6 éthylthio-5 pyrimidine, en remplaçant initialement le diéthylsulfoxyde par le dibut-ylsulfoxyde.The 2,4,4,6-butylthio-pyrimidine trichloro used as a starting product is prepared according to the process described in Example 6 for the preparation of the 2,4,4,6-ethylthio-pyrimidine trichloro, initially replacing the diethylsulfoxide with dibut-ylsulfoxide.

EXEMPLE 8 - Mélange de chloro-6 diamino-2,4 méthylthio-5 pyrimidine (isomère A) et chloro-2 diamino-4,6 méthylthio-5 pyrimidine (isomère B).EXAMPLE 8 Mixture of 6-chloro-2,4-diamino-5-methylthio-pyrimidine (isomer A) and 2-chloro-4,4-diamino-methyl-5-pyrimidine (isomer B).

Dans un autoclave.de 5 litres, on introduit 2,5 litres de méthanol, 250 g d'ammoniac et 250 g de trichloro-2,4,6 méthylthio-5 pyrimidine. On chauffe à 100°C pendant 2 heures et concentre sous pression réduite la solution obtenue. On ajoute de l'éther au résidu obtenu. La partie insoluble dans l'éther est séparée, lavée à l'eau et séchée. On obtient ainsi 153,7 g d'un mélange des isomères A et B, dans lequel l'isomère A est prédominant. Ce mélange fend à 154°C et est caractérisé par ses spectres IR et RMN.2.5 liters of methanol, 250 g of ammonia and 250 g of 2,4,4,6-methylthio-pyrimidine are introduced into a 5 liter autoclave. The mixture is heated at 100 ° C. for 2 hours and the solution obtained is concentrated under reduced pressure. Ether is added to the residue obtained. The part insoluble in ether is separated, washed with water and dried. This gives 153.7 g of a mixture of the A and B isomers, in which the A isomer is predominant. This mixture splits at 154 ° C and is characterized by its IR and NMR spectra.

EXEMPLE 9 - Amino-4 chloro-6 diéthylamino-2 méthylthio-5 pyrimidine.EXAMPLE 9 4-Amino-6-chloro-2-diethylamino-5-methylthio pyrimidine.

Ders un ballon de 500 ml muni d'un réfrigérant, on chauffe à l'ébullition pendant 3 heures 100 g de toluène, 23 g de trichloro-2,4,6 méthylthio-5 pyrimidine et 10,1 g de triéthylamine. Par concentratinr sous pression réduite de la solution obtenue, on obtient un résidu qui est introduit dans un autoclave de 500 ml avec 350 ml de méthanol et 50 g d'ammoniac. La solution obtenue après 2 heures de réactior. à 130°C est concentrée à nouveau sous pression réduite. On obtient un résidu qu'on lave à l'eau et que l'on recristellise dans un mélange eau-alcool. On obtient ainsi 17,5 g d'amino-4 chloro-6 diéthylamino-2 métrylthio-5 pyrimidine de point de fusion 68°C, qui est caractérisée par ses spectres IR et RMN.In a 500 ml flask equipped with a condenser, the mixture is heated to the boil for 3 hours 100 g of toluene, 23 g of 2,4,4,6-trichloro-5-methylthio pyrimidine and 10.1 g of triethylamine. By concentratinr under reduced pressure of the solution obtained, a residue is obtained which is introduced into an autoclave of 500 ml with 350 ml of methanol and 50 g of ammonia. The solution obtained after 2 hours of reaction. at 130 ° C. is concentrated again under reduced pressure. A residue is obtained which is washed with water and which is recrystallized from a water-alcohol mixture. 17.5 g of 4-amino-6-chloro-2-diethylamino-5-methyl-pyrimidine of melting point 68 ° C. are thus obtained, which is characterized by its IR and NMR spectra.

EXEMPLE 10 - Méthylamino-2 amino-4 chloro-6 méthylthio-5 pyrimidine.EXAMPLE 10 2-Methylamino-4 amino-6-chloro-5-methylthio pyrimidine.

Ce composé est obtenu suivant le mode opératoire de l'exemple 1, en remplaçant dans la première étape l'éthy- lamine par la méthylamine. Il fond à 205°C et est caractérisé par ses spectres IR et RMN.This compound is obtained according to the procedure of Example 1, replacing in the first stage the ethylamine by methylamine. It melts at 205 ° C and is characterized by its IR and NMR spectra.

EXEMPLE 11 - Mélange de méthylamino-4 amino-2 chloro-6 méthylthio-5 pyrimidine et chloro-2 méthylamino-4 amino-6 méthylthio-5 pyrimidine.EXAMPLE 11 Mixture of 4-methylamino-2 amino-6-chloro-5-methylthio-pyrimidine and 2-chloro-4-methylamino-6-amino-5-methylthio-pyrimidine.

Ce mélange est obtenu suivant le mode opératoire de l'exemple 5, en remplaçant dans la première étape l'éthyla- mine par la méthylamine. Il fond à 139°C et est caractérisé par ses spectres IR et RMN.This mixture is obtained according to the procedure of Example 5, replacing in the first stage the ethylamine with methylamine. It melts at 139 ° C and is characterized by its IR and NMR spectra.

EXEMPLE 12/ - Pipéridino-2 amino-4 chloro-6 méthylthio-5 pyrimidine.EXAMPLE 12 / - Piperidino-2 amino-4 chloro-6 methylthio-5 pyrimidine.

Ce composé est obtenu suivant le mode opératoire de l'exemple 1, en remplaçant dans la 1ère étape l'éthylamine par la pipéridine. Il fond à 128°C et est caractérisé par ses spectres IR et RMN.This compound is obtained according to the procedure of Example 1, replacing in the 1st step the ethylamine with piperidine. It melts at 128 ° C and is characterized by its IR and NMR spectra.

EXEMPLE 13/ - Morpholino-2 amino-4 chloro-6 méthylthio-5 pyrimidine.EXAMPLE 13 / - Morpholino-2 amino-4 chloro-6 methylthio-5 pyrimidine.

Ce composé est obtenu suivant le mode ooératcire de l'exemple 1, en remplaçant dans le 1ère étape l'éthylamine par la morpholine. Il fond à 115°C et est caractérisé par ses spectres IR et RMN.This compound is obtained according to the ooératcire mode of Example 1, by replacing in the 1st stage the ethylamine with morpholine. It melts at 115 ° C and is characterized by its IR and NMR spectra.

EXEMPLE 14 - Acétylamino-4 diéthylamino-2 chloro-6 méthylthio-5 pyrimidine.EXAMPLE 14 Acetylamino-4 diethylamino-2 chloro-6 methylthio-5 pyrimidine.

Dans un ballon de 500ml muni d'un réfrigérant et d'une agitation, on place 250 ml d'acide acétique et 25 a d'amino-4 chloro-6 diéthylamino-2 méthylthio-5 pyrimidine préparée comme indiqué à l'exemple 9. On chauffe jusqu'à 50°C. Puis on introduit progressivement 50 ml d'anhydride acétique. Acres quoi on chauffe 30 minutes à reflux. Puis on évapore sous vide et reprend le résidu à l'eau trois fois pour hydrolyser l'excès d'anhydride acétique.In a 500 ml flask fitted with a condenser and a stirrer, 250 ml of acetic acid and 25 a of 4-amino-6-chloro-2-diethylamino-methylthio-pyrimidine, prepared as indicated in Example 9, are placed. We heat up to 50 ° C. Then 50 ml of acetic anhydride are gradually introduced. Acres which is heated for 30 minutes at reflux. Then evaporated in vacuo and the residue is taken up in water three times to hydrolyze the excess acetic anhydride.

Le produit brut obtenu est ensuite recristallisé dans l'éthanol. On obtient ainsi un produit qui fond à 72-73°C, dont l'analyse par RMN et IR confirme qu'il s'agit de l'acétylamino-4 chloro-6 diéthylamino-2 méthylthio-5 pyrimidine.The crude product obtained is then recrystallized from ethanol. A product is thus obtained which melts at 72-73 ° C., the analysis of which by NMR and IR confirms that it is acetylamino-4 chloro-6 diethylamino-2 methylthio-5 pyrimidine.

EXEMPLE 15/ - Préparation d'un mélange de diamino-2,4 chloro-6 méthylthio-5 pyrimidine (isomère A) et de diamino-4,6 chloro-2 méthylthio-5 pyrimidine (isomère B).EXAMPLE 15 / Preparation of a mixture of 2,4-diamino-6 chloro-5-methylthio-pyrimidine (isomer A) and of 4,6-diamino-chloro-2-methylthio-5 pyrimidine (isomer B).

Dans un autoclave de 5 litres, on introduit 1300 g de trichloro-2,4,6 méthylthio-5 pyrimidine, 1700 ml d'isopropa- nol et 495 g d'ammoniac. On chauffe pendant 5 heures à 100°C. Après refroidissement à la température ambiante, on recueille par filtration le précipité formé, on le lave avec 700 ml d'iso- propanol puis avec de l'eau, on le sèche. On obtient ainsi 1010 g d'un mélange de diamino-2,4 chloro-6 méthylthio-5 pyrimidine (isomère A) et de diamino-4,6 chloro-2 méthylthio-5 pyrimidine (isomère B), ce qui correspond à un rendement de 93,6 % par rapport à la trichloro-2,4,6 méthylthio-5 pyrimidine de départ.1300 g of 2,4,4,6-methylthio-pyrimidine, 1,700 ml of isopropanol and 495 g of ammonia are introduced into a 5 liter autoclave. It is heated for 5 hours at 100 ° C. After cooling to room temperature, the precipitate formed is collected by filtration, washed with 700 ml of isopropanol, then with water and dried. 1010 g of a mixture of 2,4-diamino-6 chloro-5-methylthio-pyrimidine (isomer A) and 4,6-diamino-chloro-2-methylthio-5-pyrimidine (isomer B) are thus obtained, which corresponds to a yield of 93.6% relative to the starting 2,4,4,6-methylthio-pyrimidine trichloro.

Ce mélange fond à 160°C. Son analyse par chromatographie encouche mince sur silice (élution par un mélange chloro- forme/méthanol 90/10), par chromatographie en phase gazeuse couplée avec la spectrométrie de masse, car spectrométrie dans l'infra-rouge et par résonance magnétique nucléaire du carbone 13 montre qu'il contient approximativement 89 % d' isomère A et 11 % d'isomère B.This mixture melts at 160 ° C. Its analysis by thin layer chromatography on silica (elution with a 90/10 chloroform / methanol mixture), by gas chromatography coupled with mass spectrometry, because infrared and nuclear magnetic resonance spectrometry of carbon 13 shows that it contains approximately 89% of the A isomer and 11% of the B isomer.

/EXEMPLE 16/ - Préparation de la diamino-2,4 chloro-6 méthylthio-5 pyrimidine (isomère A)/ EXAMPLE 16 / Preparation of 2,4-diamino-6-chloro-5-methylthio pyrimidine (isomer A)

10 g du mélange obtenu à l'exemple 15 sont dissous dans 85 ml d'acide chlorhydrique concentré. A la solution ob- tenue on ajoute orogressivement 55 ml d'eau. Le précipité formé est filtré, lavé à l'eau et séché. On obtient ainsi 2,5 a d'un produit qui est constitué essentiellement par l'isomère A. EXEMPLE 17/ - Préparation d'un mélange diamino-2,4 chloro-6 méthylthio-5 pyrimidine (isomère A) + diamino-4,6 chloro-2 méthylthio-5 oyrimidine (isomère B) enrichi en isomère B.10 g of the mixture obtained in Example 15 are dissolved in 85 ml of concentrated hydrochloric acid. 55 ml of water are added to the solution obtained. The precipitate formed is filtered, washed with water and dried. 2.5 a of a product are thus obtained, which essentially consists of the A isomer. EXAMPLE 17 / - Preparation of a 2,4-diamino-6-chloro-5-methylthio-pyrimidine (isomer A) + 4-diamino mixture , 6-chloro-2 methylthio-5 oyrimidine (isomer B) enriched in isomer B

1ère étape :1st step :

Dans 500 ml d'eau contenant 1,2 g de PLURONIC L 92 (agent tensio-actif non ionique constitué par un copolymère d'oxyde d'éthylène et d'oxyde de propylène) on disperse par agitation 46 g de trichloro-2,4,6 méthylthio-5 pyrimidine finement broyée. Puis on introduit en 10 minutes 170 g d'une solution aqueuse d'ammoniac à 20 %, en maintenant la température à 5°C. On laisse ensuite une nuit à la température ambiante, puis on filtre le précipité formé et le lave à l'eau. On recueille ainsi 42 g d'un produit qui est un mélange des deux composés isomères dichloro-4,6 amino-2 méthylthio-5 pyrimidine et dichloro-2,6 amino-4 méthylthio-5 pyrimidine, ainsi que le montre en particulier l'analyse par résonance magnétique nucléaire du carbone 13. 2ème étape :46 g of 2-trichloro are dispersed in 500 ml of water containing 1.2 g of PLURONIC L 92 (non-ionic surfactant consisting of a copolymer of ethylene oxide and propylene oxide), 4.6 finely ground 5-methylthio pyrimidine. Then 170 g of a 20% aqueous ammonia solution are introduced over 10 minutes, while maintaining the temperature at 5 ° C. It is then left overnight at room temperature, then the precipitate formed is filtered and washed with water. 42 g of a product are thus collected, which is a mixture of the two isomeric compounds 4,6-dichloro-2 amino-5-methylthio-pyrimidine and 2,6-dichloro-4-amino-4-methylthio-5 pyrimidine, as shown in particular l carbon 13 nuclear magnetic resonance analysis. 2nd step:

40 g du mélange obtenu dans la lère étape sont dissous dans 700 ml d'acide chlorhydrique concentré. A la solution obtenue on ajoute 200 ml d'eau. Il se forme un précipité a que l'on sépare par filtration. On ajoute au filtrat 120 ml d'eau. Il se forme un nouveau précipité b que l'on sépare par filtration. On ajoute enfin au filtrat 260 ml d'eau puis 200 ml d'une solution N d'hydroxyde de sodium. Il se forme un précipi-10 té c que l'on sépare par filtration.40 g of the mixture obtained in the 1st stage are dissolved in 700 ml of concentrated hydrochloric acid. To the solution obtained is added 200 ml of water. A precipitate is formed which is separated by filtration. 120 ml of water are added to the filtrate. A new precipitate b is formed which is separated by filtration. Finally, 260 ml of water and then 200 ml of a sodium hydroxide solution N are added to the filtrate. A precipitate is formed which is separated by filtration.

Le précipité a (poids 6 g) est constitué essentiellement du composé dichloro-4,6 amino-2 méthylthio-5 pyrimidine. Le orécipité c (poids 17,2 g) est constitué du composé dichloro-2,6 amino-4 méthylthio-5 pyrimidine.The precipitate a (weight 6 g) consists essentially of the compound 4,6-dichloro-2 amino-5-methylthio pyrimidine. Orecipity c (weight 17.2 g) consists of the compound 2,6-dichloro-4 amino-5-methylthio pyrimidine.

3ème étape :3rd step:

Dans un autoclave on introduit 16,5 g du précipité c obtenu à la 2ème étape, 150 ml d'isopropanol et 17 g d'ammoniac. On chauffe à 100°C pendant 3 heures et 15 minutes. Après refroidissement on filtre le précipité formé. On obtient ainsi 11,3 g d'un produit qui est un mélange des deux isomères A et B. La teneur en isomère B du mélange est de 20 %.16.5 g of the precipitate c obtained in the 2nd step, 150 ml of isopropanol and 17 g of ammonia are introduced into an autoclave. The mixture is heated at 100 ° C for 3 hours and 15 minutes. After cooling, the precipitate formed is filtered. 11.3 g of a product are thus obtained, which is a mixture of the two isomers A and B. The content of isomer B in the mixture is 20%.

EXEMPLE 18 - Préparation de la diamino-2,4 chloro-6 méthylthio-5 pyrimidine (isomère A) et de la diamino-4,6 chloro-2 méthylthio-5 pyrimidine (isomère B) pures.EXAMPLE 18 Preparation of 2,4-diamino-6-chloro-5-methylthio-pyrimidine (isomer A) and of pure diamino-4,6-chloro-2-methylthio-5 pyrimidine (isomer B).

Les isomères A et B sont séparés par chromatographie liquide préparative à partir du mélange obtenu à la 3ème étape de l'exemple 17.The isomers A and B are separated by preparative liquid chromatography from the mixture obtained in the 3rd step of Example 17.

Le mélange est mis en solution dans du chloroforme additionné de 2,5 % d'éthanol et la solution est introduite en tête d'une colonne de longueur 25 cm et de diamètre intérieur 22 mm, remplie d'un gel de silice de granulométrie 5 µ connu sous la dénomination commerciale LICHROSORB Si 60 (produit commercialisé par la société Merck). On élue avec du chloroforme additionné de 2,5 % d'éthanol. Les fractions recueillies en queue de colonne à l'aide d'un collecteur de fractions sont évaporées. On obtient ainsi 2,1 g de chloro-6 diamino-2,4 méthylthio-5 pyrimidine, dont le point de fusion est 171°C, et 0,9 g de chloro-2 diamino-4,6 méthylthio-5 pyrimidine, dont le point de fusion est 270°C.The mixture is dissolved in chloroform supplemented with 2.5% ethanol and the solution is introduced at the head of a column 25 cm long and 22 mm inside diameter, filled with a silica gel of particle size 5 µ known under the trade name LICHROSORB Si 60 (product sold by the company Merck). Eluted with chloroform supplemented with 2.5% ethanol. The fractions collected at the bottom of the column using a fraction collector are evaporated. 2.1 g of chloro-6 diamino-2,4 methylthio-5 pyrimidine, whose melting point is 171 ° C., and 0.9 g of chloro-2 diamino-4,6 methylthio-5 pyrimidine are thus obtained, whose melting point is 270 ° C.

EXEMPLE 19 - Dans cet exemple, les produits selon l'invention sont formulés sous forme de suspensions aqueuses contenant 5 ‰ d'un tension-actif dénommé "TWEEN 20".EXAMPLE 19 In this example, the products according to the invention are formulated in the form of aqueous suspensions containing 5 ‰ of an active-tension called "TWEEN 20".

Les quantités de suspensions appliquées équivalent à 1 000 1/ha, et les dilutions réalisées sont calculées de façon à apporter les quantités de matière active suivantes :

Figure imgb0020
The quantities of suspensions applied are equivalent to 1000 1 / ha, and the dilutions carried out are calculated so as to provide the following quantities of active material:
Figure imgb0020

Les suspensions sont appliquées par pulvérisation soit sur plantes âgées de 10 jours, ce qui permet d'étudier l'action de post-levée des produits, soit sur semences déposées à la surface du sol, ce qui permet d'étudier l'action de pré-levée. Ces semences sont recouvertes de 2 cm de terre juste après l'application.The suspensions are applied by spraying either on 10-day-old plants, which makes it possible to study the post-emergence action of the products, or on seeds deposited on the soil surface, which makes it possible to study the action of pre-emergence. These seeds are covered with 2 cm of soil just after application.

Les plantes et graines sont disposées dans des conteneurs en plastique de 18x12x5 cm remplis d'une terre standard composée de 3 parties de sable, 1 partie de terreau et 1 partie d'argile. Après traitement, les conteneurs sont disposés sur une tablette à irrigation automatique dans une serre maintenue à 22°C et à un taux d'hygrométrie de 70The plants and seeds are placed in 18x12x5 cm plastic containers filled with standard soil made up of 3 parts of sand, 1 part of potting soil and 1 part of clay. After treatment, the containers are placed on an automatic irrigation tablet in a greenhouse maintained at 22 ° C and a humidity rate of 70

Les plantes soumises aux essais sont le blé TRITICUM SP, le haricot PHASEOLUS SP, la betterave BETA SP, la moutarde SINAPIS SP, le pissenlit TARAXACUM SP et le mais ZEA SP.The plants tested are TRITICUM SP wheat, PHASEOLUS SP beans, BETA SP beet, SINAPIS SP mustard, TARAXACUM SP dandelion and ZEA SP corn.

On relève les résultats 14 jours après le traitement pour les essais de post-levée et 21 jours après le trai- tement pour les essais de pré-levée.The results are noted 14 days after the treatment for the post-emergence trials and 21 days after the treatment for the pre-emergence trials.

Les résultats sont rassemblés dans le tableau No. I. Dans ce tableau l'efficacité herbicide des composés selon l'invention vis-à-vis des plantes testées est exprimée par un chiffre qui représente le pourcentage de destruction des plantes dans les lots traités. Ce pourcentage est évalué en prenant comme référence les plantes de lots témoins non traités. Le chiffre 0 indique donc que l'état des plantes est le même dans les lots traités et dans les lots témoins, le chiffre 100 que les plantes sont entièrement détruites dans les lots traités, ce qui correspond à l'efficacité maximum.The results are collated in Table No. I. In this table the herbicidal efficacy of the compounds according to the invention with respect to the plants tested is expressed by a figure which represents the percentage of destruction of the plants in the treated batches. This percentage is evaluated by taking as a reference the plants from untreated control lots. The number 0 therefore indicates that the condition of the plants is the same in the treated lots and in the control lots, the number 100 that the plants are completely destroyed in the treated lots, which corresponds to maximum efficiency.

EXEMPLE 20 -EXAMPLE 20 -

On conduit les essais comme à l'exemple 19. Seules changent les doses de matière active appliquées. Ces doses sont les suivantes :

Figure imgb0021
The tests are carried out as in Example 19. Only the doses of active ingredient applied change. These doses are as follows:
Figure imgb0021

Les résultats sont rassemblés dans les tableaux II et III. Les chiffres figurant dans ces tableaux représentent les énergies végétatives des plantes des lots traités, exprimées en pourcentage de l'énergie végétative des plantes des témoins non traités. Le chiffre 100 indique donc que l'énergie végétative des plantes des lots traités est identique à celle des plantes des témoins, le chiffre 0 que les plantes sont entièrement détruites dans les lots traités.The results are collated in Tables II and III. The figures appearing in these tables represent the vegetative energies of the plants of the treated batches, expressed as a percentage of the vegetative energy of the plants of the untreated controls. The number 100 therefore indicates that the vegetative energy of the plants in the treated lots is identical to that of the control plants, the number 0 that the plants are entirely destroyed in the treated lots.

Dans les tableaux II et III figurent également les résultats relatifs à un herbicide de référence (chlortoluron).Tables II and III also show the results for a reference herbicide (chlortoluron).

EXEMPLE 21 -EXAMPLE 21 -

On conduit les essais comme à l'exemple 19, avec les doses suivantes de matière active :

Figure imgb0022
The tests are carried out as in Example 19, with the following doses of active material:
Figure imgb0022

Les plantes soumises aux essais sont le blé TRITICUM SP, l'orge ORDEUM SP, l'avoine AVENA SP, le riz ORYZA SP, le coton GOSSYPIUM SP, le sétaire SETARIA SP, le panic PANICUM SP, la digitaire PASPALUM SP et le soja. Le composé selon l'intention testé est celui de l'exemple 8.The plants tested are TRITICUM SP wheat, ORDEUM SP barley, AVENA SP oats, ORYZA SP rice, GOSSYPIUM SP cotton, SETARIA SP foxtail, PANICUM SP panic, PASPALUM SP crabgrass and soybeans . The compound according to the intention tested is that of Example 8.

Les résultats obtenus sont rassemblés dans le tableau IV. La signification des chiffres du tableau IV est la même que celle des chiffres du tableau I. Le chiffre 0 indique que l'état des plantes est le même dans les lots traités et dans les lots témoins, le chiffre 100 que les plantes sont entièrement détruites dans les lots traités.The results obtained are collated in Table IV. The meaning of the figures in Table IV is the same as that of the figures in Table I. The number 0 indicates that the condition of the plants is the same in the treated lots and in the control lots, the figure 100 that the plants are entirely destroyed in the treated lots.

EXEMPLE 22 -EXAMPLE 22 -

Le produit de l'exemple 8 est appliqué en plein champ, par pulvérisation, sur les plantes cultivées (blé, courgette, orge, fève, soja, tournesol, colza, mais, avoine, pois, tomate) et les plantes adventices indésirables (chenopode, amarante, morelle, mercuriale, laiteron, liseron, seneçon, sétaire), soit en pré-levée des plantes immédiatement après les semis, soit en post-levée des plantes 15 jours après les semis. Les doses en produit appliquées sont 2,5 ou 5 kg/ha.The product of Example 8 is applied in the field, by spraying, on cultivated plants (wheat, zucchini, barley, broad beans, soybeans, sunflowers, rapeseed, corn, oats, peas, tomatoes) and unwanted weeds (chenopod , amaranth, nightshade, nightshade, milkweed, bindweed, seneçon, foxtail), either in pre-emergence of the plants immediately after sowing, or in post-emergence of the plants 15 days after sowing. The applied product doses are 2.5 or 5 kg / ha.

Les résultats sont notés 7, 14 et 100 jours après le traitement (J + 7; J + 14; J + 100). Ces résultats sont consignés dans le tableau V. Les chiffres figurant dans ce tableau indiquent, dans le cas des plantes cultivées, l'énergie végétative des plantes des parcelles traitées par rapport à celle des plantes des parcelles témoins non traitées et, dans le cas des plantes adventices, le pourcentage de destruction des plantes dans les parcelles traitées, ce pourcentage étant évalué en prenant comme référence les plantes de parcelles témoins non traitées.The results are noted 7, 14 and 100 days after the treatment (D + 7; D + 14; D + 100). These results are recorded in Table V. The figures appearing in this table indicate, in the case of cultivated plants, the vegetative energy of the plants of the treated plots compared to that of the plants of the untreated control plots and, in the case of the weeds, the percentage of plant destruction in the treated plots, this percentage being evaluated by taking as a reference the plants from untreated control plots.

Pour une plante cultivée, la note 100 signifie donc que l'énergie végétative de la plante est la même dans les parcelles traitées et dans les parcelles témoins et la note 0 que la plante est entièrement détruite dans les parcelles traitées.For a cultivated plant, the note 100 therefore means that the vegetative energy of the plant is the same in the treated plots and in the control plots and the note 0 that the plant is entirely destroyed in the treated plots.

Pour une plante adventice, la note 0 signifie que l'état de la plante est le même dans les parcelles traitées et les parcelles témoins et la note 100 que la plante est entièrement détruite dans les parcelles traitées.For an adventitious plant, the note 0 means that the state of the plant is the same in the treated plots and the control plots and the note 100 that the plant is entirely destroyed in the treated plots.

EXEMPLE 23 -EXAMPLE 23 -

Le produit de l'exemple 8 est appliqué par pulvérisation sur des cultures de blé d'automne de la variété Lutin, à différents stades de la culture (pré-levée, 3 feuilles, tallage, fin de tallage). Les doses en produit appliquées sont 0,625 ou 1,25 kg/ha.The product of Example 8 is applied by spraying on winter wheat crops of the Lutin variety, at different stages of the culture (pre-emergence, 3 leaves, tillering, end of tillering). The applied product rates are 0.625 or 1.25 kg / ha.

20, 22, 35, 65 et 100 jours après le traitement suivant les cas ( voir à ce sujet le tableau VI), on examine l'effet du traitement d'une part sur la plante cultivée (blé), d'autre part sur les plantes adventices indésirables (véronique, paturin, vulpin, mouron, capselle).20, 22, 35, 65 and 100 days after the treatment depending on the case (see Table VI on this subject), the effect of the treatment is examined on the one hand on the cultivated plant (wheat), on the other hand on unwanted weeds (speedwell, bluegrass, black pine, chickweed, capsella).

Dans aucun cas on n'a enregistré de phyto- toxicité vis-à-vis du blé. Dans le tableau VI sont rassemblés les résultats relatifs au taux de destruction des plantes adventices. La note 0 correspond à une plante indemne, la note 100 à une plante entièrement détruite.

Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
 In no case has phytotoxicity been recorded against wheat. In Table VI are collected the results relating to the rate of destruction of weeds. The note 0 corresponds to a free plant, the note 100 to a completely destroyed plant.
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028

Claims (12)

1 °)Composés de formule :
Figure imgb0029
dans laquelle R1 est un groupe alkyle ayant 1 à 5 atomes de carbone, l'un des substituants X1, X2, X3 est un atome de chlore ou un de brome, et les deux autres sont respectivement des groupes
Figure imgb0030
dans lesquels R2 et R3 sont, indépendamment l'un de l'autre, des atomes d'hydrogène ou des groupes alkyle de 1 à 5 atomes de carbone, cycloalkyle, aryle, aryle substitué ou
Figure imgb0031
R étant un atome d'hydrogène ou un groupe alkyle de 1 à 5 atomes de carbone, ou forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique azoté autre que les radicaux pipérazino et pirérazino substitué, R4 et R5 sont, indépendamment l'un de l'autre, des atomes d'hydrogène ou des groupes alkyle de 1 à 5 atomes de carbone, cycloalkyle, aryle, aryle substitué ou
Figure imgb0032
R étant tel que défini ci-dessus, ou forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique azoté autre que les radicaux pipérazino et pipérazino substitué, l'un au moins des substituants
Figure imgb0033
étant un groupe NH2 ou
Figure imgb0034
et leurs sels avec les acides minéraux ou organiques.1 °) Compounds of formula:
Figure imgb0029
 wherein R 1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X 1 , X 2 , X 3 is a chlorine atom or a bromine atom, and the other two are groups respectively
Figure imgb0030
 in which R 2 and R 3 are, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or
Figure imgb0031
 R being a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, or together with the nitrogen atom to which they are linked form a heterocyclic nitrogen radical other than the piperazino and substituted pirerazino radicals, R 4 and R 5 are, independently of one another, hydrogen atoms or alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, substituted aryl or
Figure imgb0032
 R being as defined above, or together with the nitrogen atom to which they are linked form a heterocyclic nitrogen radical other than the piperazino and substituted piperazino radicals, at least one of the substituents
Figure imgb0033
 being an NH 2 group or
Figure imgb0034
 and their salts with mineral or organic acids. 2°) Composés selon la revendication 1, caractérisés en ce que X1 est un atome de chlore, l'un des substituants X2 et X3 est un groupe NH2 ou
Figure imgb0035
et l'autre est un groupé NH2,
Figure imgb0036
monoalkylamino ou dialkylamino dans lesquels les chaînes alkyle ont 1 à 5 atomes de carbone, pipéridino ou morpholino.2) Compounds according to Claim 1, characterized in that X 1 is a chlorine atom, one of the substituents X 2 and X 3 is an NH 2 group or
Figure imgb0035
 and the other is an NH 2 group ,
Figure imgb0036
 monoalkylamino or dialkylamino in which the alkyl chains have 1 to 5 carbon atoms, piperidino or morpholino. 3°) Composés selon la revendication 2, caractérisés en ce que X1 est un atome de chlore, l'un des substituants X2 et X3 est un groupe NH2 ou
Figure imgb0037
et l'autre est un groupe méthylamino, éthylamino, isopropylamino, amino, diéthylamino, pipéridino ou morpholino.3 °) Compounds according to claim 2, characterized in that X 1 is a chlorine atom, one of the substituents X 2 and X 3 is an NH 2 group or
Figure imgb0037
 and the other is a methylamino, ethylamino, isopropylamino, amino, diethylamino, piperidino or morpholino group. 4°) Le composé diamino-2,4 chloro-6 méthylthio-5 pyrimidine4 °) The compound 2,4-diamino-chloro-6 methylthio-5 pyrimidine 5°) Mélanges de composés pyrimidiniques isomères selon la revendication 1.5) mixtures of isomeric pyrimidine compounds according to claim 1. 6°) Procédé de préparation des composés de formule (I) dans lesquels R2, R3, R4, R5 ne sont pas
Figure imgb0038
caractérisé en ce que on condense une trihalo-2,4,6 alkylthio-5 pyrimidine de formule :
Figure imgb0039
dans laquelle X est un atome de chlore ou de brome et R1 est un groupe alkyle ayant 1 à 5 atomes de carbone, avec un composé de formule
Figure imgb0040
dans laquelle R2 et R3 ont les mêmes significations que dans la revendication 1 excepté la signification
Figure imgb0041
et condense la dihalo-4,6 (ou-2,6) alkylthio-5 pyrimidine ainsi obtenue avec un composé de formule
Figure imgb0042
dans laquelle R4 et R5 ont les mêmes significations que dans la revendication 1 excepté la signification
Figure imgb0043
l'un au moins des composés
Figure imgb0044
étant l'ammoniac.6 °) Process for the preparation of the compounds of formula (I) in which R 2 , R 3 , R 4 , R 5 are not
Figure imgb0038
 characterized in that a 2,4,6-trihalo-5-alkylthio pyrimidine is condensed with the formula:
Figure imgb0039
 in which X is a chlorine or bromine atom and R 1 is a alkyl group having 1 to 5 carbon atoms, with a compound of formula
Figure imgb0040
 wherein R 2 and R 3 have the same meanings as in claim 1 except the meaning
Figure imgb0041
 and condenses the 4,6-dihalo (or-2,6) -5-alkylthio-pyrimidine thus obtained with a compound of formula
Figure imgb0042
 in which R 4 and R 5 have the same meanings as in claim 1 except the meaning
Figure imgb0043
 at least one of the compounds
Figure imgb0044
 being ammonia. 7°) Procédé de préparation des composé de formule (I) dans lesquels X1 est un atome de chlore ou de brome, X3 est un groupe NH2 et X est un groupe
Figure imgb0045
dans lequel R2 et R3 sont des groupe alkyle identiques R' caractérisé en ce que on fait réagir une trihalo-2,4,6 alkylthio-5 pyrimidine de formule :
Figure imgb0046
dans laquelle X est un atome de chlore ou de brome et R1 est un groupe alkyle ayant 1 à 5 atomes de carbone, avec une amine tertiaire de formule N(R')3 et condense la dihalo-4,6 alkylthio-5 pyrimidine ainsi obtenue avec l'ammoniac.7 °) Process for the preparation of the compounds of formula (I) in which X 1 is a chlorine or bromine atom, X 3 is an NH 2 group and X is a group
Figure imgb0045
 in which R 2 and R 3 are identical alkyl groups R ′ characterized in that a 2,4-trihalo-5,6-alkylthio-pyrimidine of formula:
Figure imgb0046
 in which X is a chlorine or bromine atom and R 1 is an alkyl group having 1 to 5 carbon atoms, with a tertiary amine of formula N (R ') 3 and condenses 4,6-dihalo-5-alkylthio pyrimidine thus obtained with ammonia. 8°) Procédé de préparation des composés de formule (I) dans lesquels l'un au moins de R2, R3, R4, R5 est un groupe
Figure imgb0047
caractérisé en ce que on fait réagir un composé de formule (I) dans lequel R2, R3, R4, RS ne sont pas
Figure imgb0048
avec un agent d'acylation.8 °) Process for the preparation of the compounds of formula (I) in which at least one of R 2 , R 3 , R 4 , R 5 is a group
Figure imgb0047
 characterized in that a compound of formula (I) is reacted in which R 2 , R 3 , R 4 , R S are not
Figure imgb0048
 with an acylating agent. 9°) Application en tant qu'herbicides des produits définis dans chacune des revendications 1 à 5.9 °) Application as herbicides of the products defined in each of claims 1 to 5. 10°) Compositions herbicides caractérisées en ce qu'èlles contiennent, à titre de matière active, un ou plusieurs composés tels que définis dans chacune des revendications 1 à 4. 11°) Compositions herbicides caractérisées en ce qu'elles contiennent, à titre de matière active, un ou plusieurs composés tels que définis dans chacune des revendications 1 à 4 et au moins un autre herbicide.10 °) herbicidal compositions characterized in that they contain, as active material, one or more compounds as defined in each of claims 1 to 4. 11 °) herbicidal compositions characterized in that they contain, as active ingredient, one or more compounds as defined in each of claims 1 to 4 and at least one other herbicide. 12°) Compositions herbicides selon chacune des revendications 10 et 11, caractérisées en ce que le composé inclus comme matière active est la diéthylamino-2 acétylamino-4 chloro-6 méthylthio-5 pyrimidine.12 °) herbicidal compositions according to each of claims 10 and 11, characterized in that the compound included as active material is 2-diethylamino-4-acetylamino-6-chloro-5-methylthio-pyrimidine. 13°) Compositions herbicides selon chacune des revendications 10 et 11, caractérisées en ce que le composé inclus comme matière active est la diamino-2,4 chloro-6 méthylthio-5 pyrimidine ou un mélange de diamino-2,4 chloro-6 méthylthio-5 pyrimidine et de diamino-4,6 chloro-2 méthylthio-5 pyrimidine dans lequel la diamino-2,4 chloro-6 méthylthio-5 pyrimidine prédomine.13 °) herbicidal compositions according to each of claims 10 and 11, characterized in that the compound included as active material is 2,4-diamino-chloro-6 methylthio-5 pyrimidine or a mixture of diamino-2,4 chloro-6 methylthio -5 pyrimidine and diamino-4,6 chloro-2 methylthio-5 pyrimidine in which diamino-2,4 chloro-6 methylthio-5 pyrimidine predominates.
EP78400062A 1977-07-28 1978-07-21 Amino-2 (or -4) alkylthio-5 pyrimidines, processes for their preparation, their use as herbicides and composition containing them Expired EP0000681B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR7723222A FR2398737A1 (en) 1977-07-28 1977-07-28 AMINO-2 (OR -4) ALKYLTHIO-5 PYRIMIDINES HERBICIDES
FR7723222 1977-07-28
FR7804207 1978-02-15
FR7804207A FR2417507A2 (en) 1977-07-28 1978-02-15 DIAMINO-2,4 (OR -4,6) METHYLTHIO-5 PYRIMIDINES HERBICIDES

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EP0000681A1 true EP0000681A1 (en) 1979-02-07
EP0000681B1 EP0000681B1 (en) 1981-08-26

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Cited By (11)

* Cited by examiner, † Cited by third party
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EP0013636A1 (en) * 1979-01-16 1980-07-23 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions containing 2,4-diamino-6-chloro-5-methylthio-pyrimidine and herbicidal urea derivatives and method of treatment of cultures with said compositions
FR2449403A2 (en) * 1979-02-23 1980-09-19 Ugine Kuhlmann PROCESS FOR THE HERBICIDE TREATMENT OF SORGHO USING 2,4-DIAMINO-6 CHLORO-6 METHYLTHIO-5 PYRIMIDINE
EP0021939A1 (en) * 1979-06-20 1981-01-07 P C U K Produits Chimiques Ugine Kuhlmann Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides
EP0027075A1 (en) * 1979-10-09 1981-04-15 P C U K Produits Chimiques Ugine Kuhlmann 5-Alkylsulfinyl pyrimidines, process for their preparation and their uses as herbicides
EP0024260A3 (en) * 1979-08-15 1981-05-20 Ciba-Geigy Ag Pyrimidine compounds, their preparation, herbicidal compositions containing them as active compounds and intermediates thereof
EP0070219A1 (en) * 1981-07-10 1983-01-19 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions based on 4-amino-6-chloro-5-alkylthiopyrimidine derivatives and 2,6-dinitroaniline derivatives, and method of treating crops with said compositions
EP0080917A1 (en) * 1981-11-24 1983-06-08 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions based on 4-amino-6-chloro-5-alkylthio-pyrimidine derivatives and pyridate, and process for the treatment of corps with the aid of said compositions
EP0116961A1 (en) * 1983-02-18 1984-08-29 CELAMERCK GmbH & Co. KG Pyrimidine derivatives
US4507146A (en) * 1982-12-28 1985-03-26 Ciba-Geigy Corporation 2,4-Diamino-6-halo-5-trifluoromethylpyrimidines having herbicidal activity
US4614532A (en) * 1984-05-10 1986-09-30 Bayer Aktiengesellschaft 2,4-diamino-6-halogeno-5-alkylthio-pyrimidines
EP0191443A3 (en) * 1985-02-13 1986-10-29 Basf Aktiengesellschaft 4-amino-pyrimidines and fungicides containing them

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JPS5427580A (en) * 1977-08-02 1979-03-01 Mitsui Toatsu Chem Inc Selective herbicides
FR2474279A1 (en) * 1980-01-29 1981-07-31 Ugine Kuhlmann HERBICIDE COMPOSITIONS BASED ON 2,4-DIAMINO-6 CHLORO-6 METHYLTHIO PYRIMIDINE AND DICLOFOP METHYL AND PROCESS FOR TREATING CROPS USING SAID COMPOSITIONS
FR2503162A1 (en) * 1981-04-07 1982-10-08 Pharmindustrie NOVEL PIPERAZINO-2 PYRIMIDINE DERIVATIVES, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS MEDICAMENTS OR AS INTERMEDIATES FOR THE PRODUCTION OF MEDICAMENTS
EP0078623A1 (en) * 1981-10-29 1983-05-11 Fbc Limited Herbicidal mixtures comprising benazolin

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FR2119234A5 (en) * 1970-12-24 1972-08-04 Ugine Kuhlmann 5-alkylthio amino halopyrimidines - fungicides herbicides insecticides and bactericides
FR2173746A1 (en) * 1972-03-01 1973-10-12 Ugine Kuhlmann
BE841390A (en) * 1974-05-23 1976-11-03 2,4-DIAMINO-5-CHLORO-6 PYRIMIDINES FOR USE AS MEDICINAL PRODUCTS AND PROCESS FOR THEIR PREPARATION

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FR2257294B1 (en) * 1973-07-06 1977-07-01 Ugine Kuhlmann
US3892554A (en) * 1969-02-14 1975-07-01 Sandoz Ltd 2-Amino-4-isopropylamino-6-chloro-pyrimidine in maize, wheat, potatoes, onions and leeks
US3926997A (en) * 1971-05-17 1975-12-16 Ciba Geigy Corp 2-Alkylthio-4,6-bis(substituted amino)-5-nitropyrimidines
FR2244520B1 (en) * 1973-07-06 1977-02-04 Ugine Kuhlmann
GB1523274A (en) * 1974-08-05 1978-08-31 Ici Ltd Herbicidal compositions containing substituted pyrimidine
US4166852A (en) * 1974-08-09 1979-09-04 Produits Chimiques Ugine Kuhlmann Piperazino-pyrimidines and their use as spasmolytic agents
FR2281117A2 (en) * 1974-08-09 1976-03-05 Ugine Kuhlmann NEW PIPERAZINO-PYRIMIDINES FOR USE AS MEDICINAL PRODUCTS
FR2311776A1 (en) * 1975-05-23 1976-12-17 Sogeras 2,4-DIAMINO-5-CHLORO-6 PYRIMIDINES AND PROCESS FOR THEIR PREPARATION
CH617833A5 (en) * 1975-07-07 1980-06-30 Ciba Geigy Ag
JPS6053023B2 (en) * 1977-01-25 1985-11-22 三井東圧化学株式会社 selective herbicide
JPS5427580A (en) * 1977-08-02 1979-03-01 Mitsui Toatsu Chem Inc Selective herbicides

Patent Citations (3)

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FR2119234A5 (en) * 1970-12-24 1972-08-04 Ugine Kuhlmann 5-alkylthio amino halopyrimidines - fungicides herbicides insecticides and bactericides
FR2173746A1 (en) * 1972-03-01 1973-10-12 Ugine Kuhlmann
BE841390A (en) * 1974-05-23 1976-11-03 2,4-DIAMINO-5-CHLORO-6 PYRIMIDINES FOR USE AS MEDICINAL PRODUCTS AND PROCESS FOR THEIR PREPARATION

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013636A1 (en) * 1979-01-16 1980-07-23 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions containing 2,4-diamino-6-chloro-5-methylthio-pyrimidine and herbicidal urea derivatives and method of treatment of cultures with said compositions
FR2449403A2 (en) * 1979-02-23 1980-09-19 Ugine Kuhlmann PROCESS FOR THE HERBICIDE TREATMENT OF SORGHO USING 2,4-DIAMINO-6 CHLORO-6 METHYLTHIO-5 PYRIMIDINE
EP0021939A1 (en) * 1979-06-20 1981-01-07 P C U K Produits Chimiques Ugine Kuhlmann Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides
EP0024260A3 (en) * 1979-08-15 1981-05-20 Ciba-Geigy Ag Pyrimidine compounds, their preparation, herbicidal compositions containing them as active compounds and intermediates thereof
EP0027075A1 (en) * 1979-10-09 1981-04-15 P C U K Produits Chimiques Ugine Kuhlmann 5-Alkylsulfinyl pyrimidines, process for their preparation and their uses as herbicides
FR2467201A1 (en) * 1979-10-09 1981-04-17 Ugine Kuhlmann ALKYLSULFINYL-5 PYRIMIDINES, PROCESS FOR PREPARING THEM AND USES THEREOF AS HERBICIDES
EP0070219A1 (en) * 1981-07-10 1983-01-19 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions based on 4-amino-6-chloro-5-alkylthiopyrimidine derivatives and 2,6-dinitroaniline derivatives, and method of treating crops with said compositions
EP0080917A1 (en) * 1981-11-24 1983-06-08 P C U K Produits Chimiques Ugine Kuhlmann Herbicidal compositions based on 4-amino-6-chloro-5-alkylthio-pyrimidine derivatives and pyridate, and process for the treatment of corps with the aid of said compositions
US4507146A (en) * 1982-12-28 1985-03-26 Ciba-Geigy Corporation 2,4-Diamino-6-halo-5-trifluoromethylpyrimidines having herbicidal activity
EP0116961A1 (en) * 1983-02-18 1984-08-29 CELAMERCK GmbH & Co. KG Pyrimidine derivatives
US4614532A (en) * 1984-05-10 1986-09-30 Bayer Aktiengesellschaft 2,4-diamino-6-halogeno-5-alkylthio-pyrimidines
EP0160908A3 (en) * 1984-05-10 1986-11-20 Bayer Ag 2,4-diamino-6-halogen-5-alkylthio-pyrimidines
US4640923A (en) * 1984-05-10 1987-02-03 Bayer Aktiengesellschaft Methods of combatting fungi employing 2,4-diamino-6-halogeno-5-alkylthio-pyrimidines
EP0191443A3 (en) * 1985-02-13 1986-10-29 Basf Aktiengesellschaft 4-amino-pyrimidines and fungicides containing them

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IE781533L (en) 1979-01-28
PL111645B1 (en) 1980-09-30
IT1160555B (en) 1987-03-11
IL55114A0 (en) 1978-09-29
AT368137B (en) 1982-09-10
HU182516B (en) 1984-01-30
BR7804860A (en) 1979-04-24
NZ187808A (en) 1981-01-23
DD147042A5 (en) 1981-03-18
ATA516378A (en) 1981-10-15
CA1116599A (en) 1982-01-19
GR64849B (en) 1980-06-04
YU178678A (en) 1983-02-28
CS209533B2 (en) 1981-12-31
IN149476B (en) 1981-12-19
EP0000681B1 (en) 1981-08-26
DD140040A5 (en) 1980-02-06
ES479668A1 (en) 1979-08-01
FR2417507A2 (en) 1979-09-14
RO75259A (en) 1980-11-30
IL55114A (en) 1983-11-30
JPS5427586A (en) 1979-03-01
YU40529B (en) 1986-02-28
ES472182A1 (en) 1979-10-01
AT367044B (en) 1982-05-25
US4528026A (en) 1985-07-09
IE47879B1 (en) 1984-07-11
DK300578A (en) 1979-01-29
PL114968B1 (en) 1981-03-31
FR2417507B2 (en) 1981-07-10
DE2860979D1 (en) 1981-11-19
RO79383A (en) 1982-06-25
AU3839378A (en) 1980-01-31
PL208647A1 (en) 1979-06-04
ATA46181A (en) 1982-01-15
RO79382A (en) 1982-06-25
PT68259A (en) 1978-08-01
AU520722B2 (en) 1982-02-25

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