methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate | 943831-44-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate
• 英文别名: methyl 4-acetamido-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate；methyl 4-acetamido-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate
• CAS: 943831-44-5
• 化学式: C₁₆H₁₃Cl₂FN₂O₄
• 分子量: 387.195
• InChiKey: PFDJLYKMYMHPMM-UHFFFAOYSA-N

物化性质

• 沸点：
  559.0±50.0 °C(Predicted)
• 密度：
  1.428±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate 在 水 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 以93.5%的产率得到氟氯吡啶酸
  参考文献：
  名称：

  PROCESSES FOR THE ISOLATION OF 4-AMINO-3-CHLORO-6-(4-CHLORO-2-FLUORO-3-METHOXYPHENYL)PYRIDINE-2-CARBOXYLIC ACID

  摘要：

  制备和分离4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸的过程。

  公开号：

  US20140171652A1
• 作为产物：
  描述：

  4-氨基-3,6-二氯吡啶-2-甲酸 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium fluoride 、 硫酸 作用下， 以 水 、 乙腈 为溶剂， 反应 40.33h， 生成 methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate
  参考文献：
  名称：

  The discovery of Arylex™ active and Rinskor™ active: Two novel auxin herbicides

  摘要：

  Multiple classes of commercially important auxin herbicides have been discovered since the 1940s including the aryloxyacetates (2,4-D, MCPA, dichlorprop, mecoprop, triclopyr, and fluroxypyr), the benzoates (dicamba), the quinoline-2-carboxylates (quinclorac and quinmerac), the pyrimidine-4-carboxylates (aminocyclopyrachlor), and the pyridine-2-carboxylates (picloram, clopyralid, and aminopyralid). In the last 10 years, two novel pyridine-2-carboxylate (or picolinate) herbicides were discovered at Dow AgroSciences. This paper will describe the structure activity relationship study that led to the discovery of the 6-aryl-picolinate herbicides Arylex (TM) active (2005) and Rinskor (TM) active (2010). While Arylex was developed primarily for use in cereal crops and Rinskor is still in development primarily for use in rice crops, both herbicides will also be utilized in additional crops. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2015.08.011
• 作为试剂：
  描述：

  氟氯吡啶酯 、 、 methyl 4-acetamido-3,6-dichloropicolinate 在 methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate 作用下， 以to produce methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate (Compound 4), which的产率得到methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate
  参考文献：
  名称：

  METHODS OF PRODUCING METHYL 4-AMINO-3-CHLORO-6-(4-CHLORO-2-FLUORO-3-METHOXYPHENYL)PYRIDINE-2-CARBOXYLATE

  摘要：

  制备甲基4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯的方法。其中一种方法包括将甲基异丁酮加入含有4-氯-2-氟-3-甲氧基苯基硼酸的水溶液中，形成包含4-氯-2-氟-3-甲氧基苯基硼酸和水相的有机相。将有机相和水相分离。将4-氯-2-氟-3-甲氧基苯基硼酸与甲基4-(乙酰氨基)-3,6-二氯吡啶-2-羧酸甲酯在甲基异丁酮中反应，生成甲基4-(乙酰氨基)-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯，经脱乙酰化反应制得甲基4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯。

  公开号：

  US20130172566A1

文献信息

• 6-(Poly-substituted aryl)-4-aminopicolinates and their use as herbicides
  申请人：Balko W. Terry

  公开号：US20070179060A1

  公开（公告）日：2007-08-02

  4-Aminopicolinic acids having tri- and tetra-substituted aryl substituents in the 6-position, and their amine and acid derivatives, are potent herbicides demonstrating a broad spectrum of weed control.

  在6位具有三取代和四取代芳基取代基的4-氨基吡啶酸及其胺和酸衍生物是一类高效除草剂，展示出广泛的杂草控制谱。
• 2-SUBSTITUTED-6-AMINO-5-ALKYL, ALKENYL OR ALKYNYL-4-PYRIMIDINECARBOXYLIC ACIDS AND 6-SUBSTITUTED-4-AMINO-3- ALKYL, ALKENYL OR ALKYNYL PICOLINIC ACIDS AND THEIR USE AS HERBICIDES
  申请人：Epp Jeffrey B.

  公开号：US20090088322A1

  公开（公告）日：2009-04-02

  6-Amino-4-pyrimidinecarboxylic acids having alkyl, alkenyl or alkynyl substituents in the 5-position and 4-aminopicolinic acids having alkyl, alkenyl or alkynyl substituents in the 3-position, and their amine and acid derivatives, are potent herbicides demonstrating a broad spectrum of weed control.

  在5位上具有烷基、烯基或炔基取代基的6-氨基-4-嘧啶羧酸，以及在3位上具有烷基、烯基或炔基取代基的4-氨基吡啶羧酸，以及它们的胺和酸衍生物，是表现出广谱除草作用的有效除草剂。
• [EN] METHODS OF FORMING 4-CHLORO-2-FLUORO-3-SUBSTITUTED-PHENYLBORONIC ACID PINACOL ESTERS AND METHODS OF USING THE SAME<br/>[FR] PROCÉDÉS DE FORMATION D'ESTERS PINACOLIQUES D'ACIDE 4-CHLORO-2-FLUORO-3-SUBSTITUÉ-PHÉNYLBORONIQUE ET LEURS PROCÉDÉS D'UTILISATION
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2013101665A1

  公开（公告）日：2013-07-04

  Methods include formation of 4-chloro-2 fluoro-3 substituted-phenylboronic acid pinacol esters. The method comprises contacting a 1-chloro-3-fluoro-2-substituted benzene with an alkyl lithium to form a lithiated 1-chloro-3-fluoro-2-substituted benzene. The lithiated 1-chloro-3-fluoro-2-substituted benzene is contacted with an electrophilic boronic acid derivative to form a 4-chloro-2-fluoro-3-substituted-phenylboronate. The 4-chloro-2-fluoro-3-substituted-phenylboronate is reacted with an aqueous base to form a (4-chloro-2-fluoro-3-substituted phenyl)trihydroxyborate. The (-chloro-2-fluoro-3-substituted phenyl)trihydroxyborate is reacted with an acid to form a 4-chloro-2-fluoro-3-substituted phenylboronic acid. The 4-chloro-2-fluoro-3-substituted phenylboronic acid is reacted with 2,3 dimethyl 2,3 butanediol to form 4-chloro-2-fluoro-3-substituted phenylboronic acid pinacol esters. Methods of using 4-chloro-2-fluoro-3-substituted phenylboronic acid pinacol esters to produce 6 (4-chloro-2-fluoro-3-substituted phenyl) 4 aminopicolinates are also disclosed.

  方法包括形成4-氯-2-氟-3-取代苯硼酸皮纳醇酯。该方法包括将1-氯-3-氟-2-取代苯与烷基锂接触，形成锂化的1-氯-3-氟-2-取代苯。然后将锂化的1-氯-3-氟-2-取代苯与亲电性硼酸衍生物接触，形成4-氯-2-氟-3-取代苯硼酸酯。接着将4-氯-2-氟-3-取代苯硼酸酯与水性碱反应，形成(4-氯-2-氟-3-取代苯)三羟基硼酸酯。将(-氯-2-氟-3-取代苯)三羟基硼酸酯与酸反应，形成4-氯-2-氟-3-取代苯硼酸。最后，将4-氯-2-氟-3-取代苯硼酸与2,3-二甲基-2,3-丁二醇反应，形成4-氯-2-氟-3-取代苯硼酸皮纳醇酯。此外，还披露了使用4-氯-2-氟-3-取代苯硼酸皮纳醇酯制备6-(4-氯-2-氟-3-取代苯)4-氨基吡啶酸酯的方法。
• [EN] METHODS OF PRODUCING METHYL 4-AMINO-3-CHLORO-6-(4-CHLORO-2-FLUORO-3-METHOXYPHENYL)PYRIDINE-2-CARBOXYLATE<br/>[FR] PROCÉDÉS DE FABRICATION DE 4-AMINO-3-CHLORO-6-(4-CHLORO-2-FLUORO-3-MÉTHOXYPHÉNYL)PYRIDINE-2-CARBOXYLATE DE MÉTHYLE
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2013102078A1

  公开（公告）日：2013-07-04

  Methods of producing methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate. One method comprises adding methyl isobutyl ketone to an aqueous solution comprising 4-chloro-2-fluoro-3-methoxyphenyl boronic acid to form an organic phase comprising the 4-chloro-2-fluoro-3-methoxyphenylboronic acid and an aqueous phase. The organic phase and the aqueous phase are separated. The 4-chloro-2-fluoro-3-methoxyphenylboronic acid is reacted with methyl 4-(acetylamino)-3,6-dichloropyridine-2-carboxylate in methyl isobutyl ketone to produce methyl 4-(acetylamino)-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate, which is deacetylated to produce methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate.

  生产甲基4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯的方法。其中一种方法包括将甲基异丁基酮加入含有4-氯-2-氟-3-甲氧基苯基硼酸的水溶液中，形成含有4-氯-2-氟-3-甲氧基苯基硼酸和水相的有机相。将有机相和水相分离。将4-氯-2-氟-3-甲氧基苯基硼酸与甲基4-(乙酰氨基)-3,6-二氯吡啶-2-羧酸甲酯在甲基异丁基酮中反应，生成甲基4-(乙酰氨基)-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯，然后脱乙酰基生成甲基4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-羧酸甲酯。
• [EN] METHODS OF ISOLATING (4-CHLORO-2-FLUORO-3-SUBSTITUTED-PHENYL) BORONATES AND METHODS OF USING THE SAME<br/>[FR] PROCÉDÉS D'ISOLEMENT DE PHÉNYLBORONATES 4-CHLORO-2-FLUORO-3 SUBSTITUÉS ET LEURS PROCÉDÉS D'UTILISATION
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2013101987A1

  公开（公告）日：2013-07-04

  Methods of isolating a 4-chloro-2-fluoro-3-substituted-phenylboronate include adding carbon dioxide gas or carbon dioxide solid (dry ice) to a solution comprising a 4-chloro-2-fluoro-3-substituted-phenylboronate, an inert organic solvent, and at least one lithium salt to react the at least one lithium salt with the carbon dioxide gas or carbon dioxide solid (dry ice) and form a mixture comprising the 4-chloro-2-fluoro-3- substituted-phenylboronate, the inert organic solvent, and a precipitated solid. The precipitated solid may be removed from the mixture. Methods of using 4-chloro-2- fluoro-3-substituted-phenylboronates to produce methyl-4-amino-3-chloro-6-(4-chloro- 2-fluoro-3-substituted-phenyl)pyridine-2-carboxylates are also disclosed. A 4-chloro-2-fluoro-3-substituted-phenylboronate produced by one of the methods of isolating a 4-chloro-2-fluoro-3-substituted-phenylboronate is also disclosed, wherein the 4-chloro-2-fluoro-3-substituted-phenylboronate may be obtained at a yield of greater than or equal to about 90%.

  分离4-氯-2-氟-3-取代苯基硼酸酯的方法包括向包含4-氯-2-氟-3-取代苯基硼酸酯、惰性有机溶剂和至少一种锂盐的溶液中加入二氧化碳气体或二氧化碳固体（干冰），以使至少一种锂盐与二氧化碳气体或二氧化碳固体（干冰）反应并形成包含4-氯-2-氟-3-取代苯基硼酸酯、惰性有机溶剂和沉淀固体的混合物。可以从混合物中去除沉淀固体。还公开了使用4-氯-2-氟-3-取代苯基硼酸酯制备甲基-4-氨基-3-氯-6-（4-氯-2-氟-3-取代苯基）吡啶-2-羧酸甲酯的方法。还公开了一种由分离4-氯-2-氟-3-取代苯基硼酸酯的方法之一生产的4-氯-2-氟-3-取代苯基硼酸酯，其中4-氯-2-氟-3-取代苯基硼酸酯的收率可以达到大约90％或更高。