US20150183749A1 - 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation - Google Patents

5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation Download PDF

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Publication number
US20150183749A1
US20150183749A1 US14/584,347 US201414584347A US2015183749A1 US 20150183749 A1 US20150183749 A1 US 20150183749A1 US 201414584347 A US201414584347 A US 201414584347A US 2015183749 A1 US2015183749 A1 US 2015183749A1
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Prior art keywords
compound
formula
dmf
molar ratio
contacting
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Abandoned
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US14/584,347
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English (en)
Inventor
Nakyen Choy
Ronald Ross, Jr.
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Adama Makhteshim Ltd
Corteva Agriscience LLC
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Dow AgroSciences LLC
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Priority to US14/584,347 priority Critical patent/US20150183749A1/en
Publication of US20150183749A1 publication Critical patent/US20150183749A1/en
Assigned to DOW AGROSCIENCES LLC reassignment DOW AGROSCIENCES LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOY, NAKYEN, ROSS, RONALD, JR
Priority to US15/173,493 priority patent/US9850215B2/en
Assigned to ADAMA MAKHTESHIM LTD. reassignment ADAMA MAKHTESHIM LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOW AGROSCIENCES LLC
Priority to US15/813,562 priority patent/US20180072686A1/en
Priority to US16/448,633 priority patent/US20190308941A1/en
Priority to US16/585,239 priority patent/US20200024238A1/en
Priority to US16/741,026 priority patent/US10919864B2/en
Abandoned legal-status Critical Current

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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
    • 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
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C07D333/10—Thiophene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • N3-substituted-N1-sulfonyl-5-fluoropyrimidinone fungicides and related compounds e.g., by the use of reagents and/or chemical intermediates and isolation and purification techniques which provide improved time and cost efficiency.
  • R 1 is selected from:
  • R 2 is selected from:
  • a base such as an alkali carbonate, e.g., sodium-, potassium-, cesium-, and lithium carbonate (Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , and Li 2 CO 3 , respectively) or an alkali alkoxide, for example, potassium tert-butoxide (KO t Bu) and an alkylating agent, such as an alkyl halide of Formula R 2 —X, wherein R 2 is as previously defined and X is a halogen, e.g., iodine, bromine, and chlorine, in a polar solvent, such as N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile (CH 3 CN), and the like, at concentrations from about 0.1 molar (M) to about 3 M.
  • a base such as an alkali carbonate, e.
  • a molar ratio of compounds of Formula II to the base is from about 3:1 to about 1:1 and a molar ratio of compounds of Formula II to alkylating agent is from about 1:1 to about 3:1.
  • molar ratios of compounds of Formula II to the base and compounds of Formula II to the alkylating agent of about 2:1 and 1:3, respectively, are used.
  • the reactions are conducted at temperatures between ⁇ 78° C. and 90° C., and in other embodiments, the reactions are conducted between 22° C. and 60° C.
  • compositions comprising mixtures of compounds of Formulas II and III are preferred, as isolation and purification can be achieved through precipitation and recrystallization, and the intermediate compounds of Formula II can be recovered and recycled.
  • compositions comprising mixtures of compounds of Formulas III and IV require chromatographic separation to give III along with the undesired dialkylated by-product of Formula IV.
  • the desired crude composition i.e., mixtures of compounds of Formula II and compounds of Formula III, wherein R 1 is methoxy (OCH 3 ) and R 2 is methyl (CH 3 )
  • R 1 is methoxy
  • R 2 is methyl
  • the desired crude composition is obtained through contacting a compound of Formula II with Li 2 CO 3 and methyl iodide (CH 3 I) in DMF (1.0 M) in a molar ratio of about 1:0.6:3 at 45° C.
  • the ratio of CH 3 CN:DMF is about 1:2 and the ratio of 2.5% aqueous Na 2 S 2 O 3 :DMF is about 1:1
  • the resultant solid is further purified by crystallization/precipitation from a warmed solution, about 30° C.-40° C., of the solid in a solution of a polar, aprotic solvent, such as CH 3 CN, by the addition of water (H 2 O), wherein the ratio of H 2 O:CH 3 CN is from about 1:2 to about 3:1, to give the purified compound of Formula III, and in another embodiment the ratio of H 2 O:CH 3 CN to affect precipitation of pure III is about 2:1.
  • compounds of Formula II may be prepared by contacting compounds of Formula I (shown below) with bis-N,O-trimethylsilylacetamide (BSA) at an elevated temperature, such as 70° C., for a period of about 1 hour (h), followed by cooling and contacting the solution containing the protected pyrimidinol with a substituted benzene sulfonyl chloride, generalized by R 1 —PhSO 2 Cl, wherein R 1 is as previously defined, at about 20° C.-25° C.
  • BSA bis-N,O-trimethylsilylacetamide
  • the molar ratio of the compound of Formula I to BSA and the sulfonyl chloride is about 1:3:1.1, respectively, and in another embodiment reducing the molar ratio of the reactants to about 1:1.1:1.1 affords improved yields.
  • alkyl refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • alkenyl refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.
  • aryl refers to any aromatic, mono- or bi-cyclic, containing heteroatoms.
  • heterocycle refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms.
  • alkoxy refers to an —OR substituent.
  • halogen refers to one or more halogen atoms, defined as F, Cl, Br, and I.
  • haloalkyl refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.
  • references to the compounds of Formulas I, II, III, and IV are read as also including optical isomers and salts.
  • Exemplary salts may include: hydrochloride, hydrobromide, hydroiodide, and the like.
  • the compounds of Formulas I, II, III, and IV may include tautomeric forms.
  • a method of making a compound of Formula III includes contacting a compound of Formula II with an alkali carbonate and an alkylating agent; and forming a compound of Formula III,
  • R 1 is selected from the group consisting of:
  • R 2 is selected from the group consisting of:
  • the contacting step is carried out between 22° C. and 60° C.
  • the contacting step further includes a solvent selected from the group consisting of DMF, DMSO, DMA, NMP, and CH 3 CN.
  • the alkali carbonate is selected from the group consisting of: Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , and Li 2 CO 3 .
  • the alkylating agent is selected from the group consisting of: alkyl halides and benzyl halides.
  • the alkyl halide and benzyl halide are selected from methyl iodide (CH 3 I), ethyl iodide (C 2 H 5 I), and benzyl bromide (BnBr).
  • the alkali carbonate base is Cs 2 CO 3
  • the solvent is DMF
  • a molar ratio of Compound II to alkali carbonate base is from about 3:1 to about 1:1 and a molar ratio of Compound II to alkylating agent is from about 1:1 to about 3:1.
  • a molar ratio of Compound II to alkali carbonate base is about 2:1 a molar ratio of Compound II to alkylating agent is 1:3.
  • the method further includes the step of diluting a completed reaction mixture with CH 3 CN and 2.5% aqueous Na 2 S 2 O 3 .
  • a ratio of DMF to CH 3 CN is from about 1:1 to about 3:1 and a ratio of DMF to 2.5% aqueous Na 2 S 2 O 3 is from about 1:2 to about 2:1.
  • a ratio of DMF to CH 3 CN is about 2:1 and a ratio of DMF to 2.5% aqueous Na 2 S 2 O 3 is about 1:1.
  • a method of preparing a compound of Formula II includes contacting a compound of Formula I with bis-N,O-trimethylsilylacetamide (BSA):
  • a molar ratio of compound I to bis-N,O-trimethylsilylacetamide (BSA) is 1:1.1 and the contacting step is carried out at about 22° C. to about 70° C.
  • the contacting step further includes contacting compound I with CH 3 CN.
  • the method comprises contacting a BSA treated reaction mixture with an arylsulfonyl chloride.
  • a molar ratio of Compound I to arylsulfonyl chloride is from about 1:2 to about 2:1. In an even more particular embodiment, a molar ratio of Compound I to arylsulfonyl chloride is 1:1.1.
  • the filter cake was washed with aqueous CH 3 CN (10% CH 3 CN in H 2 O) and air dried for 2 h.
  • the cake was dissolved in CH 3 CN (15 mL) at 40° C. and the solution was treated with H 2 O (30 mL).
  • the resulting suspension was cooled to room temperature, stirred for 2.5 h, and filtered.
  • the filter cake was again washed with 10% aqueous CH 3 CN and then dried under vacuum at 50° C.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
US14/584,347 2013-12-31 2014-12-29 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation Abandoned US20150183749A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US14/584,347 US20150183749A1 (en) 2013-12-31 2014-12-29 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US15/173,493 US9850215B2 (en) 2013-12-31 2016-06-03 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1 H)-one and processes for their preparation
US15/813,562 US20180072686A1 (en) 2013-12-31 2017-11-15 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/448,633 US20190308941A1 (en) 2013-12-31 2019-06-21 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/585,239 US20200024238A1 (en) 2013-12-31 2019-09-27 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/741,026 US10919864B2 (en) 2013-12-31 2020-01-13 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation

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Application Number Priority Date Filing Date Title
US201361922582P 2013-12-31 2013-12-31
US201361922572P 2013-12-31 2013-12-31
US14/584,347 US20150183749A1 (en) 2013-12-31 2014-12-29 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation

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US14/584,368 Abandoned US20150183750A1 (en) 2013-12-31 2014-12-29 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US14/584,347 Abandoned US20150183749A1 (en) 2013-12-31 2014-12-29 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US15/173,529 Active US9840476B2 (en) 2013-12-31 2016-06-03 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation
US15/173,493 Active US9850215B2 (en) 2013-12-31 2016-06-03 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1 H)-one and processes for their preparation
US15/813,562 Abandoned US20180072686A1 (en) 2013-12-31 2017-11-15 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/448,633 Abandoned US20190308941A1 (en) 2013-12-31 2019-06-21 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/585,239 Abandoned US20200024238A1 (en) 2013-12-31 2019-09-27 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/741,026 Active US10919864B2 (en) 2013-12-31 2020-01-13 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation

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US15/173,529 Active US9840476B2 (en) 2013-12-31 2016-06-03 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation
US15/173,493 Active US9850215B2 (en) 2013-12-31 2016-06-03 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1 H)-one and processes for their preparation
US15/813,562 Abandoned US20180072686A1 (en) 2013-12-31 2017-11-15 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/448,633 Abandoned US20190308941A1 (en) 2013-12-31 2019-06-21 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/585,239 Abandoned US20200024238A1 (en) 2013-12-31 2019-09-27 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation
US16/741,026 Active US10919864B2 (en) 2013-12-31 2020-01-13 5-fluoro-4-imino-3(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation

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EP (4) EP3097096A4 (enExample)
JP (3) JP6804297B2 (enExample)
CN (4) CN111362881A (enExample)
AP (1) AP2016009342A0 (enExample)
AU (2) AU2014373959B2 (enExample)
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WO2017155090A1 (en) * 2016-03-11 2017-09-14 Sumitomo Chemical Company, Limited Synergistic fungicidal composition for controlling plant diseases
US9840475B2 (en) 2012-12-28 2017-12-12 Adama Makhteshim Ltd. N-(substituted)-5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxamide derivatives
US9840476B2 (en) 2013-12-31 2017-12-12 Adama Makteshim Ltd. 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one and processes for their preparation
US9908855B2 (en) 2012-12-28 2018-03-06 Adama Makhteshim Ltd. N-(substituted)-5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxylate derivatives
US10045534B2 (en) 2013-12-31 2018-08-14 Adama Makhteshim Ltd. Synergistic fungicidal mixtures and compositions comprising 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one for fungal control
US10059703B2 (en) 2012-12-31 2018-08-28 Adama Makhteshim Ltd. 3-alkyl-5-fluoro-4-substituted-imino-3,4-dihydropyrimidin-2(1H)-one derivatives as fungicides
WO2019038583A1 (en) * 2017-07-17 2019-02-28 Adama Makhteshim Ltd. 5-FLUORO-4-IMINO-3-METHYL-1-TOSYL-3,4-DIHYDROPYRIMIDIN-2-ONE POLYMORPHS
WO2021059160A1 (en) * 2019-09-23 2021-04-01 Adama Makhteshim Ltd. Process for preparing 5-(fluoro-4-imino-3-methyl)-1-tosyl-3,4 dihydropyrimidine -(1h)-one
WO2021181274A1 (en) * 2020-03-09 2021-09-16 Adama Makhteshim Ltd. Process for preparing 5-fluoro-4-imino-3-methyl-1-(toluene-4-sulfonyl)-3,4-dihydro-1h-pyrimidin-2-one
WO2024194833A1 (en) * 2023-03-23 2024-09-26 Adama Makhteshim Ltd. Process for preparing 5-fluoro-4-imino-3-methyl-1-(toluene-4-sulfonyl)-3,4-dihydro-1h-pyrimidin-2-one

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UY36964A (es) 2015-10-27 2017-05-31 Bayer Cropscience Ag Combinaciones de principios activos que comprenden un derivado de (tio) carboxamida y un compuesto funguicida
BR112021008755A2 (pt) 2018-11-05 2021-08-10 Adama Makhteshim Ltd. misturas e composições contendo 5-fluoro-4-imino-3- metil-1-tosil-3,4-dihidropirimidina-2-ona, e métodos de uso.
MX2022000944A (es) 2019-07-22 2022-04-06 Adama Makhteshim Ltd Combinaciones, mezclas y composiciones fungicidas y usos de las mismas.
MX2022013874A (es) * 2020-05-04 2022-11-30 Adama Makhteshim Ltd Mezclas y composiciones que comprenden 5-fluoro-4-imino-3- metil-1-tosil-3,4-dihidropirimidin-2-ona, y metodos de uso de las mismas.
IL299711A (en) 2020-07-08 2023-03-01 Adama Makhteshim Ltd Fungicidal mixtures
US20240172750A1 (en) 2021-01-27 2024-05-30 Adama Makhteshim Ltd. 5-Fluoro-4-Imino-3-Methyl-1-Tosyl-3,4-Dihydropyrimidin-2(1H)-One for Controlling Plant Diseases
EP4334291A1 (en) 2021-05-04 2024-03-13 Adama Makhteshim Ltd. Crystalline forms of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4- dihydropyrimidin-2-one, and mixtures, compositions and methods of use thereof
US20240351990A1 (en) 2021-09-15 2024-10-24 Adama Makhteshim Ltd. Process for preparing 5-fluoro-4-imino-3-methyl-1-(toluene-4- sulfonyl)-3,4-dihydro-1h-pyrimidin-2-one
WO2023166485A1 (en) 2022-03-03 2023-09-07 Adama Makhteshim Ltd. Fungicidal combinations, mixtures and compositions and uses thereof
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CN114599639A (zh) * 2019-09-23 2022-06-07 阿达玛马克西姆有限公司 用于制备5-(氟-4-亚氨基-3-甲基)-1-甲苯磺酰基-3,4-二氢嘧啶-(1h)-酮的方法
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