Classifications

• • 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)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (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 Condensed Heterocyclic Rings (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

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• 1978
  • 1978-02-15 FR FR7804207A patent/FR2417507A2/fr active Granted
  • 1978-07-03 DK DK300578A patent/DK300578A/da not_active Application Discontinuation
  • 1978-07-06 PT PT68259A patent/PT68259A/pt unknown
  • 1978-07-07 NZ NZ187808A patent/NZ187808A/xx unknown
  • 1978-07-10 IL IL55114A patent/IL55114A/xx unknown
  • 1978-07-17 AT AT0516378A patent/AT367044B/de not_active IP Right Cessation
  • 1978-07-21 DE DE7878400062T patent/DE2860979D1/de not_active Expired
  • 1978-07-21 EP EP78400062A patent/EP0000681B1/de not_active Expired
  • 1978-07-25 CS CS784948A patent/CS209533B2/cs unknown
  • 1978-07-25 RO RO78100776A patent/RO79382A/ro unknown
  • 1978-07-25 RO RO7894775A patent/RO75259A/ro unknown
  • 1978-07-25 RO RO78100777A patent/RO79383A/ro unknown
  • 1978-07-26 JP JP9140278A patent/JPS5427586A/ja active Pending
  • 1978-07-26 PL PL1978215527A patent/PL114968B1/pl unknown
  • 1978-07-26 PL PL1978208647A patent/PL111645B1/pl unknown
  • 1978-07-26 YU YU1786/78A patent/YU40529B/xx unknown
  • 1978-07-26 GR GR56866A patent/GR64849B/el unknown
  • 1978-07-27 CA CA000308242A patent/CA1116599A/fr not_active Expired
  • 1978-07-27 AU AU38393/78A patent/AU520722B2/en not_active Expired
  • 1978-07-27 BR BR7804860A patent/BR7804860A/pt unknown
  • 1978-07-28 HU HU78KU535A patent/HU182516B/hu unknown
  • 1978-07-28 DD DD78216615A patent/DD147042A5/de unknown
  • 1978-07-28 IE IE1533/78A patent/IE47879B1/en unknown
  • 1978-07-28 DD DD78207005A patent/DD140040A5/de unknown
  • 1978-07-28 IT IT68803/78A patent/IT1160555B/it active
  • 1978-07-28 ES ES472182A patent/ES472182A1/es not_active Expired
  • 1978-08-28 IN IN632/DEL/78A patent/IN149476B/en unknown
• 1979
  • 1979-04-17 ES ES479668A patent/ES479668A1/es not_active Expired
• 1980
  • 1980-09-30 US US06/192,564 patent/US4528026A/en not_active Expired - Lifetime
• 1981
  • 1981-02-02 AT AT0046181A patent/AT368137B/de not_active IP Right Cessation

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