AR093976A1 - Procesos para la preparacion de 4-amino-3-halo-6-picolinatos (substituidos) y 4-amino-5-fluor-3-halo-6-picolinatos (substituidos) - Google Patents

Procesos para la preparacion de 4-amino-3-halo-6-picolinatos (substituidos) y 4-amino-5-fluor-3-halo-6-picolinatos (substituidos)

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Publication number
AR093976A1
AR093976A1 ARP130104693A ARP130104693A AR093976A1 AR 093976 A1 AR093976 A1 AR 093976A1 AR P130104693 A ARP130104693 A AR P130104693A AR P130104693 A ARP130104693 A AR P130104693A AR 093976 A1 AR093976 A1 AR 093976A1
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Argentina
Prior art keywords
formula
substituted
amino
alkyl
acid
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ARP130104693A
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English (en)
Inventor
M Renga James
C Giampietro Natalie
T Whiteker Gregory
L Johnson Peter
Galliford Christopher
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Dow Agrosciences Llc
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Publication of AR093976A1 publication Critical patent/AR093976A1/es

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agronomy & Crop Science (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (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)

Abstract

Se prepara 4-amino-3-cloro-6-picolinato (substituido) del ácido diflúor acético o del ácido triflúor acético, tritilamina o t-butilamina como un grupo protector, una 3,3-dialcoxiprop-1-ina y una metilen amina substituida por una serie de pasos. Reivindicación 1: Un proceso para la preparación de un 4-amino-3-halo-6-picolinato (substituido) de la fórmula (1), en donde X representa Cl, Br o I, R¹ representa H, alquilo C₁₋₆, cicloalquilo C₃₋₆, cicloalquilalquilo C₄₋₆, heterociclo C₃₋₆, alquenilo C₂₋₄, o fenilo, arilalquilo heteroarilalquilo substituido con desde 1 a 4 substituyentes independientemente seleccionados desde halógeno, alquilo C₁₋₄, haloalquilo C₁₋₄, alcoxi C₁₋₄ o haloalcoxi C₁₋₄, R² representa H o F, y R³ representa alquilo C₁₋₁₂ o un arilalquilo C₇₋₁₁ substituido o no substituido, el cual comprende los siguientes pasos: a) contactar el ácido diflúor acético, o el ácido trifiúor acético con tritilamina o t-butilamina en la presencia de una triarilfosfina y una base de trialquilamina en solvente de tetracloruro de carbono para producir un 2,2-diflúor o 2,2,2-triflúor-N-(tritil o t-butil)-etanimidoil cloruro (fórmula (2)), en donde cada R representa CH₃ o cada una de R representa C₆H₅, y R² representa H o F; b) contactar 2,2-diflúor- o 2,2,2-triflúor-N-(tritil o t-butil)etanimidoil cloruro (fórmula (2)) con una 3,3-dialcoxiprop-1-ina (fórmula (3)) en donde R⁴ representa alquilo C₁₋₄, en la presencia de cobre(I) iodiuro, un ioduro de metal alcalino y un fosfato de metal alcalino en un solvente polar aprótico para producir un (imino)pent-2-ina dialquil acetal de la fórmula (4) en donde R, R² y R⁴ son como se definió previamente; c) ciclizar el (imino)pent-2-ina dialquil acetal de la fórmula (4) con una amina de la fórmula (5) en donde R¹ representa H, alquilo C₁₋₆, cicloalquilo C₃₋₆, cicloalquilalquilo C₄₋₆, heterociclo C₃₋₆, alquenilo C₂₋₄, o fenilo, arilalquilo o heteroarilalquilo substituido con desde 1 a 4 substituyentes independientemente seleccionados desde halógeno, alquilo C₁₋₄, haloalquilo C₁₋₄, alcoxi C₁₋₄ o haloalcoxi C₁₋₄, en la presencia de una base de metal alcalina inorgánica en un solvente polar aprótico a una temperatura desde aproximadamente la temperatura ambiente hasta aproximadamente 100ºC producir tritil- o t-butil-protegido 4-amino-6-(substituido)-piridina-2-dialquil acetal de la fórmula (6) en donde R, R¹, R² y R⁴ son como se definió previamente; d) desproteger e hidrolizar el tritil- o t-butil-protegido 4-amino-6-(substituido)-piridina-2-dialquil acetal de la fórmula (6) con un mineral ácido en un solvente polar para producir el 4-amino-6-(substituido)picolin aldehído de la fórmula (7) en donde R¹ y R² son como se definió previamente; e) oxidar el 4-amino-6-picolinaldehído (substituido) de la fórmula (7) con un clorito de metal alcalino en la presencia de un ácido inorgánico y un depurador de ácido hipocloroso en un solvente acuoso alcohólico para producir un ácido de 4-amino-6-picolínico (substituido) de la fórmula (8) en donde R¹ y R² son como se definió previamente; (f) esterificar el ácido de 4-amino-6-picolínico (substituido) de la fórmula (8) con un compuesto de la fórmula R³Y en donde Y representa OH, Cl, Br, o I, y R³ representa alquilo C₁₋₁₂ o arilalquilo C₇₋₁₁ substituido o no substituido, para producir a 4-amino-6-picolinato (substituido) de la fórmula (9) en donde R¹, R² y R³ son como se definió previamente; y g) halogenar 4-amino-6-(substituido) picolinato de la fórmula (9) con una fuente de halógeno para producir 4-amino-3-halo-6-(substituido) picolinato de la fórmula (1). Reivindicación 3: El compuesto de fórmula (2) en donde cada R representa CH₃ o cada R representa C₆H₅, y R² representa H o F. Reivindicación 4: Un compuesto de la fórmula (4) en donde cada R representa CH₃ o cada R representa C₆H₅, y R² representa H o F, y R⁴ representa alquilo C₁₋₄. Reivindicación 5: Un compuesto de la fórmula (6) en donde R¹ representa H, alquilo C₁₋₆, cicloalquilo C₃₋₆, cicloalquilalquilo C₄₋₆, heterociclo C₃₋₆, alquenilo C₂₋₄, o fenilo, arilalquil o heteroarilalquil substituido con desde 1 a 4 substituyentes independientemente seleccionados desde halógeno, alquilo C₁₋₄, haloalquilo C₁₋₄, alcoxi C₁₋₄ o haloalcoxi C₁₋₄, cada R representa CH₃ o cada R representa C₆H₅, R² representa H o F, y R⁴ representa alquilo C₁₋₄. Reivindicación 6: Un compuesto de la fórmula (7) en donde R¹ representa H, alquilo C₁₋₆, cicloalquilo C₃₋₆, cicloalquilalquilo C₄₋₆, heterociclo C₃₋₆, alquenilo C₂₋₄, o fenilo, arilalquil o heteroarilalquil substituido con desde 1 a 4 substituyentes independientemente seleccionados desde halógeno, alquilo C₁₋₄, haloalquilo C₁₋₄, alcoxi C₁₋₄ o haloalcoxi C₁₋₄, y R² representa H o F.
ARP130104693A 2012-12-13 2013-12-13 Procesos para la preparacion de 4-amino-3-halo-6-picolinatos (substituidos) y 4-amino-5-fluor-3-halo-6-picolinatos (substituidos) AR093976A1 (es)

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US201261736830P 2012-12-13 2012-12-13

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US (1) US9096526B2 (es)
EP (1) EP2931044B1 (es)
JP (1) JP2016504320A (es)
KR (1) KR20150093226A (es)
CN (1) CN105407724B (es)
AR (1) AR093976A1 (es)
AU (1) AU2013359258B2 (es)
BR (1) BR102013032078A2 (es)
CA (1) CA2894678A1 (es)
IL (1) IL239222A (es)
MX (1) MX2015007527A (es)
NZ (1) NZ708681A (es)
PL (1) PL2931044T3 (es)
RU (1) RU2658825C2 (es)
WO (1) WO2014093591A1 (es)
ZA (1) ZA201504167B (es)

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
EP2967057B1 (en) * 2013-03-15 2018-11-21 Dow AgroSciences LLC Novel 4-aminopyridine and 6-aminopyrimidine carboxylates as herbicides
TW201609651A (zh) 2013-11-12 2016-03-16 陶氏農業科學公司 用於氟化化合物之過程（一）
TW201609652A (zh) 2013-11-12 2016-03-16 陶氏農業科學公司 用於氟化化合物之過程（三）
BR102014028164A2 (pt) * 2013-11-12 2015-09-08 Dow Agrosciences Llc processo para fluoração de compostos
EP3080083A4 (en) * 2013-12-12 2017-04-19 Dow AgroSciences LLC 4-amino-6-(halo-substituted-alkyl)-picolinates and their use as herbicides
TWI726900B (zh) 2015-08-04 2021-05-11 美商陶氏農業科學公司 用於氟化化合物之過程
CN112110852B (zh) * 2019-06-20 2022-04-26 青岛清原化合物有限公司 取代的吡啶甲酸吡啶亚甲基酯衍生物及其制备方法、除草组合物和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT1246802E (pt) * 2000-01-14 2007-06-18 Dow Agrosciences Llc 4-aminopicolinatos e sua utilização como herbicidas.
AR037228A1 (es) 2001-07-30 2004-11-03 Dow Agrosciences Llc Compuestos del acido 6-(aril o heteroaril)-4-aminopicolinico, composicion herbicida que los comprende y metodo para controlar vegetacion no deseada
TW200307669A (en) * 2002-04-15 2003-12-16 Nippon Soda Co Novel oxime o-ether compound, production process thereof, and agricultural or horticultural bactericide
UA82358C2 (uk) * 2003-04-02 2008-04-10 Дау Агросайенсиз Ллс 6-алкіл або алкеніл-4-амінопіколінати гербіцидна композиція, спосіб боротьби з небажаною рослинністю
WO2006062979A1 (en) * 2004-12-06 2006-06-15 E.I. Dupont De Nemours And Company Herbicidal 6-cyclopropyl-substitute 4-aminopicolinic acid derivatives
JP5059779B2 (ja) 2006-01-13 2012-10-31 ダウ アグロサイエンシィズ エルエルシー ６−（多置換アリール）−４−アミノピコリネートおよび除草剤としてのそれらの使用
AU2011310592B2 (en) * 2010-09-29 2015-01-22 Intervet International B.V. N-heteroaryl compounds
TWI529163B (zh) * 2011-01-25 2016-04-11 陶氏農業科學公司 用於製備４－胺基－５－氟－３－鹵素－６－（經取代之）吡啶甲酸酯的方法

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PL2931044T3 (pl) 2017-12-29
NZ708681A (en) 2016-09-30
IL239222A0 (en) 2015-07-30
US20140171654A1 (en) 2014-06-19
ZA201504167B (en) 2016-11-30
IL239222A (en) 2016-06-30
EP2931044A1 (en) 2015-10-21
WO2014093591A1 (en) 2014-06-19
CN105407724B (zh) 2017-06-09
CA2894678A1 (en) 2014-06-19
AU2013359258B2 (en) 2016-02-04
BR102013032078A2 (pt) 2014-10-21
US9096526B2 (en) 2015-08-04
JP2016504320A (ja) 2016-02-12
AU2013359258A1 (en) 2014-06-19
CN105407724A (zh) 2016-03-16
KR20150093226A (ko) 2015-08-17
RU2658825C2 (ru) 2018-06-25
EP2931044B1 (en) 2017-07-05
RU2015127992A (ru) 2017-01-18
MX2015007527A (es) 2015-10-14
EP2931044A4 (en) 2016-06-15

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