1-[3-(1,3-dithian-2-yl)propyl]-3-cyano-1,4,5,6-tetrahydropyridine | 187681-93-2

• 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: 1-[3-(1,3-dithian-2-yl)propyl]-3-cyano-1,4,5,6-tetrahydropyridine
• 英文别名: 1-[3-(1,3-dithian-2-yl)propyl]-3,4-dihydro-2H-pyridine-5-carbonitrile
• CAS: 187681-93-2
• 化学式: C₁₃H₂₀N₂S₂
• 分子量: 268.447
• InChiKey: LUYZDLLEOJPQSB-UHFFFAOYSA-N

物化性质

• 沸点：
  430.6±45.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  77.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-[3-(1,3-dithian-2-yl)propyl]-3-cyano-1,4,5,6-tetrahydropyridine 在 sodium periodate 、 正丁基锂 、 氧气 作用下， 以 甲醇 为溶剂， 反应 7.5h， 生成 (+/-)-(1'S,3'R,9S,9aR)-1,3,4,6,7,8,9,9a-octahydro-2H-quinolizine-1-spiro-2'-(1',3'-dioxo-1',3'-dithiane)-9-carbonitrile
  参考文献：
  名称：

  α,β-Unsaturated Nitriles:  Stereoselective Conjugate Addition Reactions

  摘要：

  Dithiane anions undergo intramolecular conjugate additions with alpha,beta-unsaturated nitriles when a dithiane anion is tethered to N-1 of the 3-cyano-1,4,5,6-tetrahydropyridine nucleus. 3-Cyano-1-[2-(1,3-dithianyl-2-yl)ethyl]-1,4,5,6-tetrahydropyridine (1a) and the one-carbon homologue 1b cyclize in the presence of 12-crown-4 to generate indolizidine 3 and quinolizidine 9, in which the nitrile group exhibits a strong, thermodynamic preference for the axial orientation. Oxidation of Ib provides dithiane S-oxide 10 that undergoes a highly stereoselective conjugate addition to provide crystalline quinolizidine 13. The X-ray structure of 13 is reported and corroborates our ''peg-in-a-pocket'' principle for stereoselective conjugate additions with alpha,beta-unsaturated nitriles.

  DOI：

  10.1021/jo9619894
• 作为产物：
  描述：

  3-氰基吡啶 在 sodium tetrahydroborate 、 potassium hydride 作用下， 以 乙醇 为溶剂， 反应 2.5h， 生成 1-[3-(1,3-dithian-2-yl)propyl]-3-cyano-1,4,5,6-tetrahydropyridine
  参考文献：
  名称：

  α,β-Unsaturated Nitriles:  Stereoselective Conjugate Addition Reactions

  摘要：

  Dithiane anions undergo intramolecular conjugate additions with alpha,beta-unsaturated nitriles when a dithiane anion is tethered to N-1 of the 3-cyano-1,4,5,6-tetrahydropyridine nucleus. 3-Cyano-1-[2-(1,3-dithianyl-2-yl)ethyl]-1,4,5,6-tetrahydropyridine (1a) and the one-carbon homologue 1b cyclize in the presence of 12-crown-4 to generate indolizidine 3 and quinolizidine 9, in which the nitrile group exhibits a strong, thermodynamic preference for the axial orientation. Oxidation of Ib provides dithiane S-oxide 10 that undergoes a highly stereoselective conjugate addition to provide crystalline quinolizidine 13. The X-ray structure of 13 is reported and corroborates our ''peg-in-a-pocket'' principle for stereoselective conjugate additions with alpha,beta-unsaturated nitriles.

  DOI：

  10.1021/jo9619894

文献信息

• (9S,9aR)-1,3,4,6,7,8,9,9a-Octahydro-2H-quinolizine-1-spiro-2'-(1',3'-dithiane)-9-carbonitrile
  作者：Z. Hussain、F. F. Fleming、R. E. Norman、S. C. Chang

  DOI：10.1107/s0108270195014016

  日期：1996.5.15

  The title compound, C13H20N2S2, was prepared during the intramolecular addition of dithiane anions to unsaturated nitriles. The octahydroquinolizine ring adopts a chair-chair conformation with the dithiane ring in a chair conformation oriented distal to the nitrile moiety.