10-amino-11-(4-methoxyphenyl)-1,4-dioxa-dispiro[4.2.4.2]tetradeca-9,11-diene-9-carbonitrile | 625844-82-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 10-amino-11-(4-methoxyphenyl)-1,4-dioxa-dispiro[4.2.4.2]tetradeca-9,11-diene-9-carbonitrile
• 英文别名: 3-Amino-2-(4-methoxyphenyl)-9,12-dioxadispiro[4.2.48.25]tetradeca-1,3-diene-4-carbonitrile
• CAS: 625844-82-8
• 化学式: C₂₀H₂₂N₂O₃
• 分子量: 338.406
• InChiKey: FVRSJIDCZLFSKI-UHFFFAOYSA-N

物化性质

• 沸点：
  584.6±50.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  10-amino-11-(4-methoxyphenyl)-1,4-dioxa-dispiro[4.2.4.2]tetradeca-9,11-diene-9-carbonitrile 在 氢气 作用下， 以99%的产率得到3-(4-methoxyphenyl)spiro[4.5]dec-3-ene-2,8-dione
  参考文献：
  名称：

  A novel synthesis of 2,4,4-trisubstituted 2-cyclopentenones by consecutive reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues

  摘要：

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of ketones and chloromethyl p-tolyl sulfoxide in three steps in high overall yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) at low temperature gave the adducts in almost quantitative yields. The adducts were then treated with LDA followed by excess lithium alpha-carbanion of the homologues of acetonitrile to afford 3,5,5-trisubstituted cyclopentadienyl enaminonitriles, which were hydrolyzed and heated under acidic conditions to give 2,4,4-trisubstituted 2-cyclopentenones in good overall yields. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.004
• 作为产物：
  描述：

  8-[Chloro-(toluene-4-sulfinyl)-methylene]-1,4-dioxa-spiro[4.5]decane 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 10-amino-11-(4-methoxyphenyl)-1,4-dioxa-dispiro[4.2.4.2]tetradeca-9,11-diene-9-carbonitrile
  参考文献：
  名称：

  A novel synthesis of 2,4,4-trisubstituted 2-cyclopentenones by consecutive reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues

  摘要：

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of ketones and chloromethyl p-tolyl sulfoxide in three steps in high overall yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) at low temperature gave the adducts in almost quantitative yields. The adducts were then treated with LDA followed by excess lithium alpha-carbanion of the homologues of acetonitrile to afford 3,5,5-trisubstituted cyclopentadienyl enaminonitriles, which were hydrolyzed and heated under acidic conditions to give 2,4,4-trisubstituted 2-cyclopentenones in good overall yields. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.004

文献信息

• A novel synthesis, including asymmetric synthesis, of 2,4,4-trisubstituted 2-cyclopentenones based on the reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues
  作者：Daisuke Wakasugi、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2004.11.040

  日期：2005.1

  Reaction of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones in high overall yields, with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) gave adducts in high to quantitative yields. The adducts were treated with LDA followed by lithium alpha-carbanion of the homologues of acetonitrile to give 3,5,5-trisubstituted enaminonitriles in good to high yields. Hydrolysis of the enaminonitriles under acidic conditions gave 2,4,4-trisubstituted 2-cyclopentenones in good yields. By using the optically active chloromethyl p-tolyl sulfoxide and unsymmetrical ketones, this procedure gave the optically pure 2,4,4-trisubstituted 2-cyclopentenones. The scope and limitations of this method and the mechanism of the reactions are also discussed. These procedures offer a new and effective method for the synthesis of 2,4,4-trisubstituted 2-cyclopentenones from four components, ketones, chloromethyl p-tolyl sulfoxide, acetonitrile, and its homologues. (C) 2004 Elsevier Ltd. All rights reserved.