1H-pyrrole-3-carboxylic acid, 2,5-dihydro-1-methyl-, ethyl ester | 35516-94-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 1H-pyrrole-3-carboxylic acid, 2,5-dihydro-1-methyl-, ethyl ester
• 英文别名: 3-carbethoxy-1-methyl-3-pyrroline；3-Ethoxycarbonyl-1-methyl-3-pyrrolin；1-methyl-2,5-dihydro-pyrrole-3-carboxylic acid ethyl ester；Ethyl 1-methyl-2,5-dihydropyrrole-3-carboxylate
• CAS: 35516-94-0
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: HLVCUQPXDCQOIN-UHFFFAOYSA-N

物化性质

• 沸点：
  204.1±28.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1H-pyrrole-3-carboxylic acid, 2,5-dihydro-1-methyl-, ethyl ester 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 various solvent(s) 为溶剂， 反应 3.5h， 生成 3-carbethoxy-1-methyl-1-azoniabicyclo[2.2.1]heptyl bromide
  参考文献：
  名称：

  β-氨基和β-铵基的分子内环化：1-氮杂双环的新合成途径

  摘要：

  用氢化三丁基锡处理1-（2-苯基硒乙基）-1，2，5，6-四氢吡啶（15）仅得到还原产物，表明5-己烯基9不愿进行闭环。如果通过在C4处引入酯基或通过其季铵盐来修饰自由基的性质，则很容易发生环化。尽管基团52给出了未被还原产物污染的1-甲基-1-氮杂双环[3.2.1。]辛基溴化物（55）的优异产率，但是21的双环产物伴随着一些还原的物质。后者中不需要的烯烃的产生可以通过使用季铵酯1-（2-溴乙基）-4-碳乙氧基-1-甲基-1,2,5,6-四氢吡啶鎓溴化物（35）消除。暴露于氢化三丁基锡，得到1：1个内酯/外酯混合物，分别是4-乙氧基-1-甲基-1-氮杂双环[3.2.1]辛基溴化物（37）。这些结果证明了当酯官能团与5-己烯基系统的双键连接时，酯官能团具有强大的极性效应，该性质可在自由基58的情况下得到利用。前体的处理，1-（2 -溴溴乙基）-3-碳乙氧基-1-甲基-3-吡咯啉溴化物（60）

  DOI：

  10.1021/jo000790v
• 作为产物：
  描述：

  聚合甲醛 、 肌氨酸 、 丙炔酸乙酯 在 magnesium sulfate 作用下， 以 甲苯 为溶剂， 反应 1.5h， 生成 1H-pyrrole-3-carboxylic acid, 2,5-dihydro-1-methyl-, ethyl ester
  参考文献：
  名称：

  .beta.-Proline analogs as agonists at the strychnine-sensitive glycine receptor

  摘要：

  3-Carboxy-3,4-dehydropyrrolidine was found to bind with affinity equal to that of glycine in a [H-3]strychnine binding assay. Simple substitution of the 1-, 2-, 4-, or 5-position resulted in marked loss of affinity. A decline in affinity was also found upon enlargement, contraction, or saturation of the 5-membered ring. However, beta-proline and azetidine-3-carboxylic acid retained significant binding affinity. Despite its good affinity in [H-3]strychnine binding, 3-carboxy-3,4-dehydropyrrolidine showed only weak agonist activity in intracellular recordings of cultured murine spinal cord neurons. This apparent lack of correlation between binding and functional results is discussed in light of the current models of the strychnine-sensitive glycine receptor.

  DOI：

  10.1021/jm00080a006

文献信息

• Regioselective 6-<i>Endo </i>Cyclization of 5-Carbomethoxy-5-hexenyl Radicals:  A Convenient Synthesis of Derivatives of the 1-Azabicyclo[2.2.1]heptyl System
  作者：Ernest W. Della、Chris Kostakis、Paul A. Smith

  DOI：10.1021/ol990557n

  日期：1999.8.1

  [GRAPHICS]Ring closure of the 5-carbomethoxy-5-hexenyl radical is governed largely by the polar effect, and as predicted by frontier molecular orbital considerations, endo cyclization predominates, leading to cyclohexyl rather than cyclopentyl- based products, In cyclization of the corresponding beta-ammonio species 18, stereoelectronic effects do not distinguish between attack of the radical center at C3 or C4, each of which represents a 5-exo ring closure. The radical 18 is found to cyclize with great rapidity and with high stereoselectivity to give bicyclo[2.2.1]heptane products in accordance with expectation based on polar effects; this transformation represents an excellent entry to the physiologically important bicyclic ester 17.
• US7351711B2
  申请人：——

  公开号：US7351711B2

  公开（公告）日：2008-04-01
• .beta.-Proline analogs as agonists at the strychnine-sensitive glycine receptor
  作者：Graham Johnson、James T. Drummond、Peter A. Boxer、Robert F. Bruns

  DOI：10.1021/jm00080a006

  日期：1992.1

  3-Carboxy-3,4-dehydropyrrolidine was found to bind with affinity equal to that of glycine in a [H-3]strychnine binding assay. Simple substitution of the 1-, 2-, 4-, or 5-position resulted in marked loss of affinity. A decline in affinity was also found upon enlargement, contraction, or saturation of the 5-membered ring. However, beta-proline and azetidine-3-carboxylic acid retained significant binding affinity. Despite its good affinity in [H-3]strychnine binding, 3-carboxy-3,4-dehydropyrrolidine showed only weak agonist activity in intracellular recordings of cultured murine spinal cord neurons. This apparent lack of correlation between binding and functional results is discussed in light of the current models of the strychnine-sensitive glycine receptor.
• Intramolecular Cyclization of β-Amino and β-Ammonio Radicals:  A New Synthetic Route to the 1-Azabicyclo[3.2.1]octyl- and -[2.2.1]heptyl Systems
  作者：Ernest W. Della、Paul A. Smith

  DOI：10.1021/jo000790v

  日期：2000.10.1

  with tributyltin hydride generates 58 which is found to cyclize with high regioselectivity, affording a convenient high-yielding synthesis of the endo/exo isomers of 3-carbethoxy-1-methyl-1-azoniabicyclo[2.2.1]heptyl bromide 57. The isomeric bicyclo[2.2.1]heptyl ester 63 was not detected. These observations are in accordance with predictions based upon frontier molecular orbital considerations.

  用氢化三丁基锡处理1-（2-苯基硒乙基）-1，2，5，6-四氢吡啶（15）仅得到还原产物，表明5-己烯基9不愿进行闭环。如果通过在C4处引入酯基或通过其季铵盐来修饰自由基的性质，则很容易发生环化。尽管基团52给出了未被还原产物污染的1-甲基-1-氮杂双环[3.2.1。]辛基溴化物（55）的优异产率，但是21的双环产物伴随着一些还原的物质。后者中不需要的烯烃的产生可以通过使用季铵酯1-（2-溴乙基）-4-碳乙氧基-1-甲基-1,2,5,6-四氢吡啶鎓溴化物（35）消除。暴露于氢化三丁基锡，得到1：1个内酯/外酯混合物，分别是4-乙氧基-1-甲基-1-氮杂双环[3.2.1]辛基溴化物（37）。这些结果证明了当酯官能团与5-己烯基系统的双键连接时，酯官能团具有强大的极性效应，该性质可在自由基58的情况下得到利用。前体的处理，1-（2 -溴溴乙基）-3-碳乙氧基-1-甲基-3-吡咯啉溴化物（60）