EP0000681B1 - Amino-2 (ou -4) alkylthio-5 pyrimidines, leurs procédés de préparation, leur application comme herbicides et compositions les contenant - Google Patents

Amino-2 (ou -4) alkylthio-5 pyrimidines, leurs procédés de préparation, leur application comme herbicides et compositions les contenant Download PDF

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Publication number
EP0000681B1
EP0000681B1 EP78400062A EP78400062A EP0000681B1 EP 0000681 B1 EP0000681 B1 EP 0000681B1 EP 78400062 A EP78400062 A EP 78400062A EP 78400062 A EP78400062 A EP 78400062A EP 0000681 B1 EP0000681 B1 EP 0000681B1
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EP
European Patent Office
Prior art keywords
pyrimidine
chloro
methylthio
formula
amino
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP78400062A
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German (de)
English (en)
French (fr)
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EP0000681A1 (fr
Inventor
Daniel Balde
Gérard Emile Marcel Boutemy
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Produits Chimiques Ugine Kuhlmann
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Produits Chimiques Ugine Kuhlmann
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Priority claimed from FR7723222A external-priority patent/FR2398737A1/fr
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Publication of EP0000681A1 publication Critical patent/EP0000681A1/fr
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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 group amino or acylamino.
  • 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, X 1 is a chlorine atom, X 2 is a group wherein R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and may be further, when R 2 is a hydrogen atom, a group in which R is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, X 3 is a group wherein R 4 is a hydrogen atom and R 5 is a hydrogen atom or a group R being as defined above.
  • the compounds of formula (I) in which R 3 and R 5 are not may be prepared by condensation of a 2,4,6,6-alkylthio-pyrimidine trichloro of formula (II), in which X is a chlorine atom and R 1 is an alkyl group having 1 to 5 carbon atoms, with a compound of formula (III), in which R 2 and R 3 have the same meanings as in formula (I) except the meaning and condensation of the 4,6-dichloro-5-alkylthio pyrimidine of formula (IV) thus obtained with a compound of formula (V), in which R 4 and R 5 have the same meanings as in formula (l) except the meaning
  • m and n are numbers greater than O and less than 1.
  • the 2,4,4,6-trichloro-5-alkylthio pyrimidines of formula (II) are known products. They can be prepared for example by the process described in French patent 1,549,494 applied for 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), when the latter this 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 hydrochloric acid HX formed in the reaction.
  • a basic agent capable of fixing the hydrochloric 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 lower than the ordinary temperature, for example between 0 and 10 ° C., or at a temperature higher than the ordinary temperature, for example between 100 and 150 ° C.
  • Reactions (2) and (2) bis cannot be carried out at temperatures as low as those which can be used for 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 5-dichloroalkylthio pyrimidines (IV) and (IV) bis isomers 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 compounds (I) bis and (I) ter, isomers of the compound (I).
  • 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) J.
  • 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 applications herbicides.
  • the isomeric compounds (I), (I) bis and (I) ter can also be separated by preparative liquid chromatography.
  • the compounds of formula (I) in which X 3 is an NH 2 group and X 2 is a group in which R 2 and R 3 are identical alkyl groups R ′ can also be prepared by reaction of a 2,4,4,6-alkylthio-pyrimidine trichloro of formula (II) with a tertiary amine of formula (VIII) and condensation 4,6-dichloro-5-alkylthio-pyrimidine of formula (IX) thus obtained with ammonia, according to the following reaction scheme:
  • Reaction (4) which has the originality of selectively providing the 4,6-dichloro-5-alkylthio-pyrimidine isomer, can be carried out in an organic solvent medium, at a temperature between 100 and 150 ° C.
  • organic solvents which can be used mention may be made of the same solvents 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 hunting 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 3 and R s is a group can be prepared by acylation of the compounds of formula (I) in which R 3 and 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 monocotyledons or dicotyledons and this at very low doses of between 150 g / ha and 2500 g / ha. In particular they totally destroy the following plants: ryegrass, panic, crabgrass, foxtail, wild oats, bedstraw, amaranth, knotweed, capsella, speedwell, mustard, datura, chickweed, stellar, thistle, fumitory, chenopoda, sorrel, plantain , atriplex, dandelion, poppy, chrysanthemum, senearme, 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.
  • the compounds of formula (I) and their salts are active with regard to adventitious plants 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 conservation, aqueous suspension, adhesion to 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 chlorine 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.
  • the synthesis is carried out in 2 steps.
  • the synthesis is carried out in two stages.
  • Chloro-6 diamino-2,4 butylthio-5 pyrimidine In a 500 ml autoclave, the mixture is heated to 100 ° C. for 2 hours, 120 g of methanol, 20 g of ammonia and 17 g of 2,4,4,6-trichloro-5-butylthio-pyrimidine. 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 I.R., R.M.N. and mass.
  • the 2,4,4,6-butylthio-pyrimidine trichloro used as starting material is prepared according to the process described in Example 5 for the preparation of the 2,4,4,6-ethylthio-pyrimidine trichloro, initially replacing the diethylsulfoxide with dibutylsulfoxide.
  • This compound is obtained according to the procedure of Example 1, replacing in the first step the ethylamine with methylamine. It melts at 205 ° C and is characterized by its I.R. and R.M.N.
  • Example 11 10 g of the mixture obtained in Example 11 are dissolved in 85 ml of concentrated hydrochloric acid. 55 ml of water are gradually added to the solution obtained. The precipitate formed is filtered, washed with water and dried. 2.9 g of a product are thus obtained, which essentially consists of the A isomer.
  • the precipitate a (weight 6 g) consists essentially of the compound dichloro-4,6 amino-2 methylthio-5-pyrimidine.
  • the precipitate 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 13.
  • 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 silica gel with a particle size of 5 y known under the trade name LICHROSORB Si 60 (product marketed by the company Merck). Eluted with chloroform added 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.
  • the products according to the invention are formulated in the form of aqueous suspensions containing 5% of a surfactant 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 18 x 12 x 5 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 at 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 I The results are collated in table 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.
  • 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 invention tested is that of Example 7.
  • 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 lots treated in the control lots, the number 100 that the plants are completely destroyed in the lots processed.
  • Example 7 The product of Example 7 is applied in the open field, by spraying, on cultivated plants (wheat, zucchini, barley, broad beans, soybeans, sunflowers, rapeseed, corn, oats, peas, tomatoes) and unwanted advantices plants (chenopod , amaranth, nightshade, nightshade, milkweed, bindweed, senezier, 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.
  • results are noted 7, 14 and 100 days after the treatment (D + 7; 7 + 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 plants weeds, the percentage of plants destroyed in the treated plots, this percentage being evaluated taking as reference the plants of untreated control plots.
  • 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 O that the plant is entirely destroyed in the treated plots.
  • the note O 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 7 The product of Example 7 is applied by spraying on winter wheat cultures 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.

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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)
EP78400062A 1977-07-28 1978-07-21 Amino-2 (ou -4) alkylthio-5 pyrimidines, leurs procédés de préparation, leur application comme herbicides et compositions les contenant Expired EP0000681B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR7723222A FR2398737A1 (fr) 1977-07-28 1977-07-28 Amino-2 (ou -4) alkylthio-5 pyrimidines herbicides
FR7723222 1977-07-28
FR7804207A FR2417507A2 (fr) 1977-07-28 1978-02-15 Diamino-2,4 (ou -4,6) methylthio-5 pyrimidines herbicides
FR7804207 1978-02-15

Publications (2)

Publication Number Publication Date
EP0000681A1 EP0000681A1 (fr) 1979-02-07
EP0000681B1 true EP0000681B1 (fr) 1981-08-26

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EP78400062A Expired EP0000681B1 (fr) 1977-07-28 1978-07-21 Amino-2 (ou -4) alkylthio-5 pyrimidines, leurs procédés de préparation, leur application comme herbicides et compositions les contenant

Country Status (24)

Country Link
US (1) US4528026A (cs)
EP (1) EP0000681B1 (cs)
JP (1) JPS5427586A (cs)
AT (2) AT367044B (cs)
AU (1) AU520722B2 (cs)
BR (1) BR7804860A (cs)
CA (1) CA1116599A (cs)
CS (1) CS209533B2 (cs)
DD (2) DD147042A5 (cs)
DE (1) DE2860979D1 (cs)
DK (1) DK300578A (cs)
ES (2) ES472182A1 (cs)
FR (1) FR2417507A2 (cs)
GR (1) GR64849B (cs)
HU (1) HU182516B (cs)
IE (1) IE47879B1 (cs)
IL (1) IL55114A (cs)
IN (1) IN149476B (cs)
IT (1) IT1160555B (cs)
NZ (1) NZ187808A (cs)
PL (2) PL111645B1 (cs)
PT (1) PT68259A (cs)
RO (3) RO75259A (cs)
YU (1) YU40529B (cs)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5427580A (en) * 1977-08-02 1979-03-01 Mitsui Toatsu Chem Inc Selective herbicides
FR2446597A2 (fr) * 1979-01-16 1980-08-14 Ugine Kuhlmann Compositions herbicides a base de diamino-2,4 chloro-6 methylthio-5 pyrimidine et de neburon
FR2449403A2 (fr) * 1979-02-23 1980-09-19 Ugine Kuhlmann Procede de traitement herbicide du sorgho utilisant la diamino-2,4 chloro-6 methylthio-5 pyrimidine
FR2459234A1 (fr) * 1979-06-20 1981-01-09 Ugine Kuhlmann Hydrazino (ou azido) alkylthio-5 pyrimidines, leurs procedes de preparation et leurs utilisations comme pesticides
US4560402A (en) * 1979-08-15 1985-12-24 Ciba Geigy Corporation 2,4-Diamo-5-(alkylsulfinyl) or alkylsulphonyl)-6-halopyrimidines
FR2467201A1 (fr) * 1979-10-09 1981-04-17 Ugine Kuhlmann Alkylsulfinyl-5 pyrimidines, leur procede de preparation et leurs utilisations comme herbicides
FR2474279A1 (fr) * 1980-01-29 1981-07-31 Ugine Kuhlmann Compositions herbicides a base de diamino-2,4 chloro-6 methylthio pyrimidine et de diclofop methyl et procede de traitement des cultures a l'aide desdites compositions
FR2503162A1 (fr) * 1981-04-07 1982-10-08 Pharmindustrie Nouveaux derives de piperazino-2 pyrimidine, procedes pour leur preparation et leur utilisation comme medicaments ou comme intermediaires pour la fabrication de medicaments
FR2509135A1 (fr) * 1981-07-10 1983-01-14 Ugine Kuhlmann Compositions herbicides a base de derives d'amino-4 chloro-6 alkylthio-5 pyrimidine et de derives de la dinitro-2,6 aniline et procede de traitement des cultures a l'aide desdites compositions
EP0078623A1 (en) * 1981-10-29 1983-05-11 Fbc Limited Herbicidal mixtures comprising benazolin
FR2516748A1 (fr) * 1981-11-24 1983-05-27 Ugine Kuhlmann Compositions herbicides a base de derives d'amino-4 chloro-6 alkylthio-5 pyrimidine et de pyridate, et procede de traitement des cultures a l'aide desdites compositions
US4507146A (en) * 1982-12-28 1985-03-26 Ciba-Geigy Corporation 2,4-Diamino-6-halo-5-trifluoromethylpyrimidines having herbicidal activity
DE3305524A1 (de) * 1983-02-18 1984-08-23 Celamerck Gmbh & Co Kg, 6507 Ingelheim Neue pyrimidinderivate
DE3417264A1 (de) * 1984-05-10 1985-11-14 Bayer Ag, 5090 Leverkusen Neue 2,4-diamino-6-halogen-5-alkylthio-pyrimidine
DE3504895A1 (de) * 1985-02-13 1986-08-14 Basf Ag, 6700 Ludwigshafen 4-aminopyrimidine und diese enthaltende fungizide

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2257294B1 (cs) * 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
FR2119234A5 (en) * 1970-12-24 1972-08-04 Ugine Kuhlmann 5-alkylthio amino halopyrimidines - fungicides herbicides insecticides and bactericides
US3926997A (en) * 1971-05-17 1975-12-16 Ciba Geigy Corp 2-Alkylthio-4,6-bis(substituted amino)-5-nitropyrimidines
FR2173746B1 (cs) * 1972-03-01 1975-04-25 Ugine Kuhlmann
FR2244520B1 (cs) * 1973-07-06 1977-02-04 Ugine Kuhlmann
US3906953A (en) * 1974-05-23 1975-09-23 American Optical Corp Endoscopic surgical laser system
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 (fr) * 1974-08-09 1976-03-05 Ugine Kuhlmann Nouvelles piperazino-pyrimidines utilisables comme medicaments
FR2311776A1 (fr) * 1975-05-23 1976-12-17 Sogeras Diamino-2,4 bromo-5 chloro-6 pyrimidines et procede pour leur preparation
CH617833A5 (cs) * 1975-07-07 1980-06-30 Ciba Geigy Ag
JPS6053023B2 (ja) * 1977-01-25 1985-11-22 三井東圧化学株式会社 選択性殺草剤
JPS5427580A (en) * 1977-08-02 1979-03-01 Mitsui Toatsu Chem Inc Selective herbicides

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YU40529B (en) 1986-02-28
IN149476B (cs) 1981-12-19
IL55114A0 (en) 1978-09-29
ATA46181A (de) 1982-01-15
PT68259A (pt) 1978-08-01
FR2417507B2 (cs) 1981-07-10
CA1116599A (fr) 1982-01-19
DD147042A5 (de) 1981-03-18
PL208647A1 (pl) 1979-06-04
AU520722B2 (en) 1982-02-25
IE47879B1 (en) 1984-07-11
ES472182A1 (es) 1979-10-01
RO79382A (ro) 1982-06-25
IE781533L (en) 1979-01-28
IL55114A (en) 1983-11-30
AT368137B (de) 1982-09-10
DK300578A (da) 1979-01-29
DD140040A5 (de) 1980-02-06
AU3839378A (en) 1980-01-31
EP0000681A1 (fr) 1979-02-07
BR7804860A (pt) 1979-04-24
JPS5427586A (en) 1979-03-01
YU178678A (en) 1983-02-28
CS209533B2 (en) 1981-12-31
FR2417507A2 (fr) 1979-09-14
RO75259A (ro) 1980-11-30
AT367044B (de) 1982-05-25
GR64849B (en) 1980-06-04
NZ187808A (en) 1981-01-23
ES479668A1 (es) 1979-08-01
IT1160555B (it) 1987-03-11
ATA516378A (de) 1981-10-15
DE2860979D1 (en) 1981-11-19
PL114968B1 (en) 1981-03-31
PL111645B1 (en) 1980-09-30
RO79383A (ro) 1982-06-25
US4528026A (en) 1985-07-09
HU182516B (en) 1984-01-30

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