4-ethyl-3-methyl-2-(p-toluenesulfonyl)-1H-pyrrole | 171111-15-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-ethyl-3-methyl-2-(p-toluenesulfonyl)-1H-pyrrole
• 英文别名: 4-ethyl-3-methyl-2-tosylpyrrole；4-ethyl-3-methyl-2-p-toluenesulfonyl-pyrrole；4-ethyl-3-methyl-2-tosyl-1H-pyrrole；4-ethyl-3-methyl-2-(4-methylphenyl)sulfonyl-1H-pyrrole
• CAS: 171111-15-2
• 化学式: C₁₄H₁₇NO₂S
• 分子量: 263.36
• InChiKey: WQVHCBXCJUWOPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  58.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-ethyl-3-methyl-2-(p-toluenesulfonyl)-1H-pyrrole 在 sodium tetrahydroborate 、 phenyltrimethylammonium tribromide 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 3-乙基-4-甲基-3-吡咯啉-2-酮
  参考文献：
  名称：

  Synthesis and properties of mesobilirubins XIIγ and XIIIγ and their mesobiliverdins

  摘要：

  The title pigments, with propionic acid groups displaced to the lactam end rings, were synthesized for the first time by the "1 + 2 + 1" approach, coupling two equivalents of a monopyrrole to a dipyrrylmethane (to give XII gamma), or the "2 + 2" approach, self-coupling two equivalents of a dipyrrinone (to give XIII gamma). Using the "1 + 2 + 1" approach, mesobilirubin III alpha was also prepared. Mesobilirubins XII gamma and XIII gamma are more polar than mesobilirubin III alpha and unlike III alpha cannot effectively engage the propionic acid groups in intramolecular hydrogen bonding to the dipyrrinone components. The new mesobilirubins give exciton coupled circular dichroism spectra in the presence of human serum albumin or quinine, with the XII gamma isomer exhibiting Cotton effect intensities nearly as strong as those from the III alpha isomer; whereas, the XIII gamma isomer exhibits far weaker intensities. Mesobilirubin III alpha requires glucuronidation for hepatobiliary elimination; whereas, XII gamma and XIII gamma do not, and they are excreted intact across the liver into bile. The corresponding biliverdins XII gamma and XIII gamma are reduced only slowly by biliverdin IX alpha reductase, in contrast to the fast reduction of the natural IX alpha isomer.

  DOI：

  10.1007/s00706-014-1160-6
• 作为产物：
  描述：

  2-(ethyloxycarbonyl)-3-ethyl-4-methylpyrrole 在 palladium on activated charcoal sodium hydroxide 、 三氯化铝 、 氢气 、 碘 、 sodium acetate 、 碳酸氢钠 、 potassium iodide 作用下， 以 甲醇 、 硝基甲烷 、 乙醇 为溶剂， 反应 8.0h， 生成 4-ethyl-3-methyl-2-(p-toluenesulfonyl)-1H-pyrrole
  参考文献：
  名称：

  从 3,4-二取代 2-吡咯羧酸乙酯开始合成 3,4-二取代的 2-甲苯磺酰吡咯和 5-甲苯磺酰-1,5-二氢-2H-吡咯-2-酮

  摘要：

  3,4-二取代的 2-tosylpyrroles 和 5-tosyl-1,5-dihydro-2H-pyrrol-2-ones 的合成是通过 3,4-二取代的 2-iodo-5-tosylpyrroles 从乙基 3,4 开始的-二取代的 2-吡咯羧酸盐。

  DOI：

  10.1246/bcsj.69.3339

文献信息

• Regioselective Oxidation of Pyrrole Derivatives with DDQ and Its Synthetic Application
  作者：Ryoji Iwamoto、Yutaka Ukaji、Katsuhiko Inomata

  DOI：10.1246/cl.2010.176

  日期：2010.3.5

  t-Butyl 4-alkyl-1H-pyrrole-2-carboxylates were oxidized with DDQ in the presence of MeOH at the α-position of the alkyl substituent at the C-4 position regioselectively to afford 4-acylpyrrole derivatives. On the other hand, treatment of the pyrroles with DDQ in the presence of AcOH furnished the corresponding 4-(1-acetoxyalkyl)pyrroles. The resulting 4-(acetoxymethyl)pyrrole reacted with various nucleophiles to afford the functionalized pyrrole derivatives in good yields.

  t-丁基4-烷基-1H-吡咯-2-羧酸酯在甲醇存在下与DDQ氧化，选择性地在C-4位的烷基取代基的α位生成4-酰基吡咯衍生物。另一方面，将吡咯与DDQ和醋酸一起处理，得到相应的4-(1-乙酰氧基烷基)吡咯。所得的4-(乙酰氧基甲基)吡咯与各种亲核试剂反应，产生功能化的吡咯衍生物，产率良好。
• An improved coupling procedure for the barton-zard pyrrole synthesis
  作者：Pavel Bobál、David A. Lightner

  DOI：10.1002/jhet.5570380239

  日期：2001.3

  final step in the Barton-Zard pyrrole synthesis uses inexpensive potassium carbonate as base in the coupling-cyclization reaction of vic-nitro-acetates with isocyanides. In this modification the isolated yields of synthetically useful 2-carboalkoxypyrroles (1a,b and 3) and 2-(p-toluenesulfonyl)pyrroles (2a,b) consistently rise to the 78-89% range. Conversion of 2a to 5-(p-toluenesulfonyl)-2-pyrrolinone

  Barton-Zard吡咯合成中改进的最终步骤在vic-硝基乙酸酯与异氰酸酯的偶联环化反应中使用廉价的碳酸钾作为碱。在该修饰中，合成上有用的2-羰基烷氧基吡咯（1a，b和3）和2-（对甲苯磺酰基）吡咯（2a，b）的分离产率始终提高到78-89％的范围。通过与30％的过氧化氢在乙酸中反应，可方便而直接地将2a转化为5-（对甲苯磺酰基）-2-吡咯烷酮4，从而避免了涉及溴化然后溶剂分解的两步程序。
• Rearrangement of Tosyl Group of 3,4-Disubstituted 2-Tosylpyrroles under Mild Acidic Conditions
  作者：Kazuhiro Kohori、Hideki Kinoshita、Katsuhiko Inomata

  DOI：10.1246/cl.1995.799

  日期：1995.9

  Tosyl group of 3,4-disubstituted 2-tosylpyrroles easily rearranged from 2- to 5-position by treatment with TFA. The ratio of the regioisomers at equilibrium was definitely influenced by the bulkiness of the substituent at 3-position of the starting 2-tosylpyrroles.

  通过用 TFA 处理，3,4-二取代的 2-tosylpyrroles 的 Tosyl 基团很容易从 2-位重排到 5-位。平衡时区域异构体的比例肯定受起始 2-甲苯磺酰基吡咯的 3-位取代基的体积影响。
• An Intramolecularly Hydrogen Bonded Dihydrotripyrrinone
  作者：Adrianne K. Tipton、David A. Lightner

  DOI：10.1007/pl00010223

  日期：1999.3

  A yellow tripyrrole analog (1) of bilirubin has been synthesized, and its lone propionic acid group is found to engage in conformation determining, intramolecular hydrogen bonding in solution and in the crystal. Molecular modelling and X-ray crystallography reveal an abbreviated ridge-tile or L-shape conformation in which an essentially planar dipyninone is hydrogen bonded to the single opposing propionic acid group. In the (arbitrary) (P)-helicity ridge-tile, the torsion angles about C(10) are computed to be 55 degrees and 61 degrees by molecular dynamics and found to be 66 degrees and 53 degrees in the crystal. Such torsion angles lead to an interplanar dihedral angle (similar to 93 degrees) between the dipyninone and its adjoining pyrrole that is very close to the dihedral angle (similar to 98 degrees) found in intramolecularly hydrogen bonded bilirubin.
• Synthesis and properties of mesobilirubins XIIγ and XIIIγ and their mesobiliverdins
  作者：Portia Mahal G. Sabido、David A. Lightner

  DOI：10.1007/s00706-014-1160-6

  日期：2014.5

  The title pigments, with propionic acid groups displaced to the lactam end rings, were synthesized for the first time by the "1 + 2 + 1" approach, coupling two equivalents of a monopyrrole to a dipyrrylmethane (to give XII gamma), or the "2 + 2" approach, self-coupling two equivalents of a dipyrrinone (to give XIII gamma). Using the "1 + 2 + 1" approach, mesobilirubin III alpha was also prepared. Mesobilirubins XII gamma and XIII gamma are more polar than mesobilirubin III alpha and unlike III alpha cannot effectively engage the propionic acid groups in intramolecular hydrogen bonding to the dipyrrinone components. The new mesobilirubins give exciton coupled circular dichroism spectra in the presence of human serum albumin or quinine, with the XII gamma isomer exhibiting Cotton effect intensities nearly as strong as those from the III alpha isomer; whereas, the XIII gamma isomer exhibits far weaker intensities. Mesobilirubin III alpha requires glucuronidation for hepatobiliary elimination; whereas, XII gamma and XIII gamma do not, and they are excreted intact across the liver into bile. The corresponding biliverdins XII gamma and XIII gamma are reduced only slowly by biliverdin IX alpha reductase, in contrast to the fast reduction of the natural IX alpha isomer.