Phenyl-piperidin-(2Z)-ylidene-acetic acid methyl ester | 560132-18-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: Phenyl-piperidin-(2Z)-ylidene-acetic acid methyl ester
• 英文别名: methyl (2Z)-2-phenyl-2-piperidin-2-ylideneacetate
• CAS: 560132-18-5
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: GKRLCEILONDACM-SEYXRHQNSA-N

物化性质

• 熔点：
  114.1-115.0 °C
• 沸点：
  392.8±42.0 °C(Predicted)
• 密度：
  1.100±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Phenyl-piperidin-(2Z)-ylidene-acetic acid methyl ester 在 盐酸 、 sodium cyanoborohydride 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 0.5h， 以90%的产率得到erythro-(2R,2'S)-methyl phenidate
  参考文献：
  名称：

  Studies on the Eschenmoser coupling reaction and insights on its mechanism. Application in the synthesis of Norallosedamine and other alkaloids

  摘要：

  The conditions of the Eschenmoser coupling reaction were studied. The formation of the alpha-thioiminium ion was achieved faster in the presence of an additive (Nal) and dry chloroform as the preferred solvent. The developed conditions were used for the second part of the reaction (the sulfur extrusion itself). The present protocol avoids the formation of byproducts, which were previously described as a major drawback to be overcome. Electrospray ionization tandem mass spectrometry was used to characterize some aspects (intermediates) of the first step of the reaction mechanism. Some reduction conditions were properly tested and the selected conditions were applied to the synthesis of the natural alkaloid Norallosedamine and other derivatives. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.01.081
• 作为产物：
  描述：

  methyl 2-phenyl-2-((3,4,5,6-tetrahydropyridin-2-yl)thio)acetate hydrobromide 在 三乙胺 、 三苯基膦 作用下， 以 氯仿 为溶剂， 反应 24.0h， 生成 2-phenyl-6,7-dihydro-5H-[1,3]thiazolo[3,2-a]pyridin-3-one 、 Phenyl-piperidin-(2Z)-ylidene-acetic acid methyl ester
  参考文献：
  名称：

  Studies on the Eschenmoser coupling reaction and insights on its mechanism. Application in the synthesis of Norallosedamine and other alkaloids

  摘要：

  The conditions of the Eschenmoser coupling reaction were studied. The formation of the alpha-thioiminium ion was achieved faster in the presence of an additive (Nal) and dry chloroform as the preferred solvent. The developed conditions were used for the second part of the reaction (the sulfur extrusion itself). The present protocol avoids the formation of byproducts, which were previously described as a major drawback to be overcome. Electrospray ionization tandem mass spectrometry was used to characterize some aspects (intermediates) of the first step of the reaction mechanism. Some reduction conditions were properly tested and the selected conditions were applied to the synthesis of the natural alkaloid Norallosedamine and other derivatives. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.01.081

文献信息

• A concise and stereoselective synthesis of (+/−)-erythro-methylphenidate
  作者：Dennis Russowsky、Brenno Amaro da Silveira Neto

  DOI：10.1016/s0040-4039(03)00420-9

  日期：2003.3

  A concise and stereoselective synthesis of racemic erythro-methylphenidate (1) is described. The coupling reaction between piperidine-2-thione (3) and 2-bromo-2-phenylmethylacetate (4) afforded the β-enaminocarbonyl compound 2 in 60% yield by a modified Eschenmoser sulfide contraction reaction. In most cases the bicyclic thiazolidinone 5 was produced. Diastereoselective reduction of 2 in the presence

  描述了外消旋的赤-甲基哌啶酯（1）的简明和立体选择性的合成。通过改进的Eschenmoser硫化物收缩反应，哌啶-2-硫酮（3）和2-溴-2-苯基甲基乙酸酯（4）之间的偶联反应以60％的产率提供了β-烯氨基羰基化合物2。在大多数情况下，产生了双环噻唑烷酮5。在存在硼氢化物的情况下，非对映选择性还原2使（+/-）-赤型-甲基哌啶酯的产率高，dr > 95％。
• The influence of the ring size of thiolactams in the Eschenmoser coupling reaction in presence of DBU. Formation of bicyclic thiazolidinones or thioimines
  作者：Dennis Russowsky、Brenno Amaro da Silveira Neto

  DOI：10.1016/j.tetlet.2003.12.049

  日期：2004.2

  The different behaviors of pyrrolidin-2-thione and piperidin-2-thione under a modified Eschenmoser sulfur contraction reaction protocol using DBU as base was observed. The pyrrolidin-2-thione lb follows the expected reaction course, leading to thioimines 5a-d. which can be transformed subsequently into the respective by action of a thiophile, while the piperidin-2-thione leads to the formation of bicyclic thiazolidinones 4b-d in moderate to good yields. The -enaminocarbonyl compound 11 was hydrogenated to afford the respective five-membered analogue of methylphenidate 12. (C) 2003 Elsevier Ltd. All rights reserved.