3-(4-Oxopentyl)benzonitrile | 103094-53-7

• 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: 3-(4-Oxopentyl)benzonitrile
• CAS: 103094-53-7
• 化学式: C₁₂H₁₃NO
• 分子量: 187.241
• InChiKey: CTOLZNGQVJIXMW-UHFFFAOYSA-N

物化性质

• 沸点：
  330.6±25.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(4-Oxopentyl)benzonitrile 在 六甲基磷酰三胺 、 samarium diiodide 、 叔丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以47%的产率得到5-hydroxy-5-methyl-5,6,7,8,-tetrahydronaphthalene-2-carbonitrile
  参考文献：
  名称：

  Substituent Effects in Samarium Diiodide-Induced 6-trig Cyclizations of γ-Arylketones to Functionalized Hexahydronaphthalene Derivatives

  摘要：

  二碘化钐诱导的取代δ-芳基酮 1、4、5、9、11 和 14 的 6 三环化反应受芳基取代基的影响很大。对位甲氧基衍生物 5 以及正、对位氰基衍生物 9 和 14 能以中等至较好的产率提供预期的官能化六氢萘衍生物 6（连同 7）、10 和 15，而正甲氧基化合物 1 是一种较差的底物，偏甲氧基衍生物 4 完全没有发生环化反应。偏氰基化合物 11 的表现比较特殊，因为中间环己二烯 "碳离子 "足够稳定，可以被亲电体捕获，从而以中等产率生成 17 和 18 等加合物。

  DOI：

  10.1055/s-2001-16051
• 作为产物：
  描述：

  间甲基苯腈 在 盐酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 3-(4-Oxopentyl)benzonitrile
  参考文献：
  名称：

  Electroreductive intramolecular coupling of nonconjugated aromatic ketones

  摘要：

  The electroreduction of nonconjugated aromatic ketones gave intramolecularly coupled products. The best result was obtained using an Sn cathode in i-PrOH containing tetraalkylammonium salt as a supporting electrolyte. This reductive cyclization proceeded with remarkable stereoselectivity, and the cis isomer was obtained exclusively. A variety of new bi- and polycyclic compounds were synthesized. The reaction mechanism was studied, and it was suggested that the anion radical generated by one-electron transfer to a carbonyl group attacks an aromatic ring intramolecularly. The choice of counter cation of the anion radical was critical for the reductive cyclization. Other reductive methods employing metal reducing agents were also studied. Reduction with Na in HMPA-THF gave the same cyclized product, though the yield was lower than that with the electroreduction.

  DOI：

  10.1021/jo00085a033

文献信息

• Lithium Bromide/Water as Additives in Dearomatizing Samarium‐Ketyl (Hetero)Arene Cyclizations
  作者：Chintada Nageswara Rao、Christoph Bentz、Hans‐Ulrich Reissig

  DOI：10.1002/chem.201502912

  日期：2015.11.2

  New conditions for dearomatizing samarium‐ketyl (hetero)arene cyclizations are reported. In many examples of these samarium diiodide‐mediated reactions, lithium bromide and water can be used as additives instead of the carcinogenic and mutagenic hexamethylphosphoramide (HMPA). The best results were obtained for the cyclizations of N‐acylated indole derivatives delivering the expected indolines in good

  据报道使sa-酮基（杂）芳烃环化脱芳香化的新条件。在这些由二碘化sa介导的反应的许多示例中，溴化锂和水可以代替致癌和诱变的六甲基磷酰胺（HMPA）用作添加剂。N-酰化吲哚衍生物的环化反应获得了最佳结果，从而以预期的产率和良好的非对映选择性提供了预期的二氢吲哚。还描述了一种新型的环化反应，可提供吲哚基取代的烯丙基衍生物。讨论了溴化锂/水系统的范围和局限性。
• Substituent Effects in Samarium Diiodide-Induced 6-trig Cyclizations of γ-Arylketones to Functionalized Hexahydronaphthalene Derivatives
  作者：Mathias Berndt、Hans-Ulrich Reissig

  DOI：10.1055/s-2001-16051

  日期：——

  The samarium diiodide-induced 6-trig cyclizations of substituted γ-arylketones 1, 4, 5, 9, 11, and 14 are strongly influenced by substituents of the aryl group. Whereas para-methoxy derivative 5 as well as ortho- and para-cyano derivatives 9 and 14 provided the expected functionalized hexahydronaphthalene derivatives 6 (together with 7), 10, and 15 in moderate to good yields, ortho-methoxy compound 1 was a poor substrate and meta-methoxy derivative 4 did not undergo cyclization at all. The behavior of meta-cyano compound 11 was exceptional since the intermediate cyclohexadienyl "carbanion" was sufficiently stable to be trapped by electrophiles furnishing adducts such as 17 and 18 in moderate yields.

  二碘化钐诱导的取代δ-芳基酮 1、4、5、9、11 和 14 的 6 三环化反应受芳基取代基的影响很大。对位甲氧基衍生物 5 以及正、对位氰基衍生物 9 和 14 能以中等至较好的产率提供预期的官能化六氢萘衍生物 6（连同 7）、10 和 15，而正甲氧基化合物 1 是一种较差的底物，偏甲氧基衍生物 4 完全没有发生环化反应。偏氰基化合物 11 的表现比较特殊，因为中间环己二烯 "碳离子 "足够稳定，可以被亲电体捕获，从而以中等产率生成 17 和 18 等加合物。
• Samarium Diiodide Mediated Ketyl-Aryl Coupling Reactions - Influence of Substituents and Trapping Experiments
  作者：Ulrike K. Wefelscheid、Mathias Berndt、Hans-Ulrich Reißig

  DOI：10.1002/ejoc.200800293

  日期：2008.7

  derivatives as single diastereoisomers in most cases. The position of the substituents was also of crucial influence on the outcome; in several cases ipso-substitution leading to the formation of spiro compounds was observed. Electron-donating substituents at the aromatic moiety are less favourable for the ketyl–aryl couplings. They apparently impede the second electron transfer that is involved in this multi-step

  这项综合研究描述了芳基部分的取代基对 SmI2 介导的分子内酮基-芳基偶联反应的影响。不同取代的γ-芳基酮被用作前体，其通过4-戊烯-2-醇与相应的溴苯或碘苯的Heck反应直接制备。在用两当量的二碘化钐γ-芳基酮处理后，带有吸电子取代基，如氰基、三氟甲基或羰基，在大多数情况下，得到预期的六氢化萘衍生物，为单一的非对映异构体。取代基的位置对结果也有至关重要的影响。在一些情况下，观察到导致形成螺环化合物的 ipso 取代。芳族部分的给电子取代基对酮基-芳基偶联不太有利。它们显然阻碍了这个多步骤过程中涉及的第二次电子转移。在这些观察的基础上，详细讨论了 SmI2 促进的酮基-芳基偶联的机制。对于在间位具有吸电子取代基的前体，SmI2 促进的环化的相当稳定的碳负离子中间体可以用丙酮或烯丙基溴作为亲电试剂捕获，以区域选择性地提供相应的加成产物。我们的结果对于立体选择性生成的六氢化萘衍生物的合成应用应该是有价值的。（©
• Electroreductive intramolecular coupling of nonconjugated aromatic ketones
  作者：Naoki Kise、Takeshi Suzumoto、Tatsuya Shono

  DOI：10.1021/jo00085a033

  日期：1994.3

  The electroreduction of nonconjugated aromatic ketones gave intramolecularly coupled products. The best result was obtained using an Sn cathode in i-PrOH containing tetraalkylammonium salt as a supporting electrolyte. This reductive cyclization proceeded with remarkable stereoselectivity, and the cis isomer was obtained exclusively. A variety of new bi- and polycyclic compounds were synthesized. The reaction mechanism was studied, and it was suggested that the anion radical generated by one-electron transfer to a carbonyl group attacks an aromatic ring intramolecularly. The choice of counter cation of the anion radical was critical for the reductive cyclization. Other reductive methods employing metal reducing agents were also studied. Reduction with Na in HMPA-THF gave the same cyclized product, though the yield was lower than that with the electroreduction.