[(5.6-Dicarboxy-pyridin-3-yl)methyl]tri-methylammonium bromide

• 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: [(5.6-Dicarboxy-pyridin-3-yl)methyl]tri-methylammonium bromide
• 英文别名: [(5,6-dicarboxy-3-pyridyl)methyl]trimethylammonium bromide；2-Carboxy-5-[(trimethylazaniumyl)methyl]pyridine-3-carboxylate;hydrobromide
• 化学式: Br*C₁₁H₁₅N₂O₄
• 分子量: 319.155
• InChiKey: RQCOFILZZCGCOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.31
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  87.5
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(5.6-Dicarboxy-pyridin-3-yl)methyl]tri-methylammonium bromide 在 sodium hydroxide 、 硫酸 、 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 生成 5-甲氧基甲基-2,3-吡啶二羧酸
  参考文献：
  名称：

  5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for

  摘要：

  提供了5,6-二取代-3-吡啶甲基铵盐化合物，一种其制备方法以及用于制备5-(取代甲基)-2,3-吡啶二羧酸的用途。

  公开号：

  US05288866A1
• 作为产物：
  描述：

  1,3-二溴-5,5-二甲基海因 、 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 、 5-甲基吡啶-2,3-二羧酸二乙基酯 在 三甲胺 作用下， 以 氯苯 为溶剂， 生成 [(5.6-Dicarboxy-pyridin-3-yl)methyl]tri-methylammonium bromide
  参考文献：
  名称：

  5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for

  摘要：

  提供了5,6-二取代-3-吡啶甲基铵盐化合物，一种其制备方法以及用于制备5-(取代甲基)-2,3-吡啶二羧酸的用途。

  公开号：

  US05288866A1

文献信息

• Process for Manufacturing Substituted 3-pyridylmethyl Ammonium Bromides
  申请人：Gebhardt Joachim

  公开号：US20110224433A1

  公开（公告）日：2011-09-15

  A process for manufacturing 5,6-disubstituted-3-pyridylmethyl ammonium bromides (I), wherein Q is a tertiary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; Z is hydrogen or halogen; Z 1 is hydrogen, halogen, cyano or nitro; Y and Y 1 are each independently OR 1 , NR 1 R 2 , or when taken together YY 1 is —O—, —S— or NR 3 —; R 1 and R 2 are each independently hydrogen, C 1 -C 4 alkyl optionally substituted with C 1 -C 4 alkoxy or phenyl optionally substituted with one to three C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups or halogen atoms, or phenyl optionally substituted with one to three C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups or halogen atoms; R 3 is hydrogen or C 1 -C 4 alkyl; comprises the steps of (i) reacting a compound of formula (II), wherein the symbols have the meaning given in formula (I), with bromine in the presence of a radical initiator in a solvent mixture comprising an aqueous phase and an organic phase, where the organic phase comprises a solvent selected from 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene and tetrachloromethane, and where the pH-value of the aqueous phase is from 3 to <8, to obtain a 3-bromomethyl-5,6-disubstituted pyridine compound (III), wherein Y, Y 1 , Z and Z 1 have the meanings given in formula (I), and (ii) reacting the bromo compound of formula (III) with a tertiary amine base Q in a solvent at a temperature range of about 0° C. to 100° C.

  一种制造5,6-二取代-3-吡啶基甲基铵溴化物（I）的方法，其中Q是三级脂肪或环状、饱和、部分不饱和或芳香胺；Z是氢或卤素；Z1是氢、卤素、氰基或硝基；Y和Y1各自独立地是OR1、NR1R2，或当一起取YY1时为-O-、-S-或NR3-；R1和R2各自独立地是氢、C1-C4烷基，可选地取代C1-C4烷氧基或苯基，可选地取代一到三个C1-C4烷基、C1-C4烷氧基或卤素原子的苯基，或可选地取代一到三个C1-C4烷基、C1-C4烷氧基或卤素原子的苯基；R3是氢或C1-C4烷基；包括以下步骤：（i）在包含水相和有机相的溶剂混合物中，有机相包括从1,2-二氯乙烷、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯和四氯化碳中选择的溶剂，水相的pH值为3到<8的条件下，在自由基引发剂的存在下，将式（II）的化合物与溴反应，得到3-溴甲基-5,6-二取代吡啶化合物（III），其中Y、Y1、Z和Z1具有式（I）中的含义，以及（ii）在溶剂中，将式（III）的溴化合物与三级胺碱Q反应，在温度范围约为0℃至100℃。
• Process for Manufacturing Substituted 5-Methoxymethylpyridine-2,3-Dicarboxylic Acid Derivatives
  申请人：Cortes David

  公开号：US20110245506A1

  公开（公告）日：2011-10-06

  A process for manufacturing a 2,3-disubstituted-5-methoxymethylpyridine of formula (I), where Z is H or halogen; Z 1 is H, halogen, CN or NO 2 ; Y 2 is OM, and M is an alkali metal or an alkaline earth metal, comprises the step of: (i) reacting a compound of formula (II) where Q is a tertiary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; Z is H or halogen; Z 1 is H, halogen, CN or NO 2 ; Y 1 and Y 2 are each independently OR 1 , NR 1 R 2 , or when taken together Y 1 Y 2 is —O—, —S— or —NR 3 —; R 1 and R 2 are each independently H, C 1 -C 4 alkyl optionally substituted with C 1 -C 1 alkoxy or phenyl optionally substituted with one to three C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups or halogen atoms, or phenyl optionally substituted with one to three C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups or halogen atoms; R 3 is H or C 1 -C 4 alkyl, in a methanol/H 2 O mixture, comprising at least 20% by weight H 2 O (based on the sum of water and bromide (II)), with a base comprising MOCH 3 and/or MOH, where M is alkali metal or alkaline earth metal, under pressure in a closed vessel at a temperature of from 75 to 110° C. Compounds of formula (I) are useful intermediates in the synthesis of herbicidal imidazolinones, like imazamox.

  一种制备式为（I）的2,3-二取代-5-甲氧甲基吡啶的工艺，其中Z为H或卤素；Z1为H、卤素、CN或NO2；Y2为OM，M为碱金属或碱土金属，包括以下步骤：（i）在甲醇/H2O混合物中，至少包含20％重量的H2O（基于水和溴化物（II）的总和），与包含MOCH3和/或MOH的碱基反应，其中M为碱金属或碱土金属，反应式为（II）的化合物，其中Q为三级脂肪族或环状、饱和、部分不饱和或芳香族胺；Z为H或卤素；Z1为H、卤素、CN或NO2；Y1和Y2各自独立地为OR1、NR1R2或当一起取时，Y1Y2为-O-、-S-或-NR3-；R1和R2各自独立地为H、C1-C4烷基（可选地取代为C1-C1烷氧基或苯基，可选地取代为一个至三个C1-C4烷基、C1-C4烷氧基或卤素原子的苯基），或苯基（可选地取代为一个至三个C1-C4烷基、C1-C4烷氧基或卤素原子），R3为H或C1-C4烷基，在封闭容器中，在温度为75至110°C的压力下进行。式（I）的化合物是合成除草剂咪唑烷酮（如伊马唑）的有用中间体。
• Process for manufacturing substituted 3-pyridylmethyl ammonium bromides
  申请人：Gebhardt Joachim

  公开号：US09096570B2

  公开（公告）日：2015-08-04

  A process for manufacturing 5,6-disubstituted-3-pyridylmethyl ammonium bromides (I), wherein Q is a tertiary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; Z is hydrogen or halogen; Z1 is hydrogen, halogen, cyano or nitro; Y and Y1 are each independently OR1, NR1R2, or when taken together YY1 is —O—, —S— or NR3—; R1 and R2 are each independently hydrogen, C1-C4 alkyl optionally substituted with C1-C4 alkoxy or phenyl optionally substituted with one to three C1-C4 alkyl groups, C1-C4 alkoxy groups or halogen atoms, or phenyl optionally substituted with one to three C1-C4 alkyl groups, C1-C4 alkoxy groups or halogen atoms; R3 is hydrogen or C1-C4 alkyl; comprises the steps of (i) reacting a compound of formula (II), wherein the symbols have the meaning given in formula (I), with bromine in the presence of a radical initiator in a solvent mixture comprising an aqueous phase and an organic phase, where the organic phase comprises a solvent selected from 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene and tetrachloromethane, and where the pH-value of the aqueous phase is from 3 to <8, to obtain a 3-bromomethyl-5,6-disubstituted pyridine compound (III), wherein Y, Y1, Z and Z1 have the meanings given in formula (I), and (ii) reacting the bromo compound of formula (III) with a tertiary amine base Q in a solvent at a temperature range of about 0° C. to 100° C.

  一种制造5,6-二取代-3-吡啶甲基溴化铵(I)的方法，其中Q是三级脂肪族或环状、饱和、部分不饱和或芳香胺；Z是氢或卤素；Z1是氢、卤素、氰基或硝基；Y和Y1各自独立地是OR1、NR1R2或当一起时YY1是—O—、—S—或NR3—；R1和R2各自独立地是氢、C1-C4烷基（可选地取代C1-C4烷氧基或苯基，可选地取代一到三个C1-C4烷基、C1-C4烷氧基或卤素原子的苯基）或苯基（可选地取代一到三个C1-C4烷基、C1-C4烷氧基或卤素原子的苯基）；R3是氢或C1-C4烷基；包括以下步骤：(i)在包含水相和有机相的溶剂混合物中，有机相包括从1,2-二氯乙烷、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯和四氯化碳中选择的溶剂，在存在自由基引发剂的情况下，将式(II)化合物与溴反应，其中符号具有式(I)中给出的含义，其中水相的pH值为3至<8，以获得3-溴甲基-5,6-二取代吡啶化合物(III)，其中Y、Y1、Z和Z1具有式(I)中给出的含义，以及(ii)将式(III)的溴化物与三级胺碱Q在溶剂中反应，在约0℃至100℃的温度范围内。
• Process for the preparation of (5,6-dicarboxy-3-pyridyl) methyl ammonium halides
  申请人：American Cyanamid Company

  公开号：EP0812828A1

  公开（公告）日：1997-12-17

  There is provided a process for the preparation of [(5,6-dicarboxy-3-pyridyl)methyl]ammonium halides having the structural formula I The [(5,6-dicarboxy-3-pyridyl)methyl]ammonium halides are useful as intermediates in the preparation of herbicidal 5-(alkoxymethyl)-2-(2-imidazolin-2-yl)nicotinic acids, esters and salts.

  提供了一种具有结构式 I 的[(5,6-二羧基-3-吡啶基)甲基]卤化铵的制备方法 该[(5,6-二羧基-3-吡啶基)甲基]卤化铵可作为中间体用于制备除草剂 5-(烷氧基甲基)-2-(2-咪唑啉-2-基)烟酸、酯和盐。
• PROCESS FOR MANUFACTURING 5-METHOXYMETHYLPYRIDINE-2,3-DICARBOXYLIC ACID DERIVATIVES
  申请人：BASF Agrochemical Products B.V.

  公开号：EP3782985A1

  公开（公告）日：2021-02-24

  An improved process for manufacturing a compound of formula (I), comprising steps (ii) and (iii): (ii) reacting a mixture of compounds of formulae (III.1), (III.2) and (III.3), with phosphorous acid (HPO(OH)2) or a phosphite selected from dimethyl phosphite and diethyl phosphite, and trimethylamine in a solvent at a temperature range of 0°C to 100°C, to obtain a compound of formula (II); and (iii) reacting the compound of formula (II) in methanol, toluene or a methanol/toluene mixture with a base selected from MOCH3 and MOH (if the solvent is methanol), where M is as defined in formula (I), to obtain the compound of formula (I).

  一种制造式 (I) 化合物的改进工艺、 包括步骤(ii)和(iii) (ii) 使式(III.1)、(III.2)和(III.3)化合物的混合物发生反应、 与亚磷酸（HPO(OH)2）或选自亚磷酸二甲酯和亚磷酸二乙酯的亚磷酸酯以及三甲胺在溶剂中于 0°C 至 100°C 的温度范围内反应，得到式（II）化合物；以及 (iii) 使式(II)化合物在甲醇、甲苯或甲醇/甲苯混合物中与选自 MOCH3 和 MOH 的碱反应（如果溶剂为甲醇），其中 M 如式(I)中所定义，得到式(I)化合物。