3,4,3',4'-tetramethoxy-N-(2-phenylethyl)phenylthioacetamide | 72527-19-6

• 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: 3,4,3',4'-tetramethoxy-N-(2-phenylethyl)phenylthioacetamide
• 英文别名: 2-(3,4-dimethoxyphenyl)-N-[2-(3,4-dimethoxyphenyl)ethyl]thioacetamide；2-(3,4-dimethoxyphenyl)-N-[2-(3,4-dimethoxyphenyl)ethyl]ethanethioamide
• CAS: 72527-19-6
• 化学式: C₂₀H₂₅NO₄S
• 分子量: 375.489
• InChiKey: UPPYLOHWYMQBKC-UHFFFAOYSA-N

物化性质

• 熔点：
  49-51 °C(Solv: ligroine (8032-32-4))
• 沸点：
  512.8±60.0 °C(Predicted)
• 密度：
  1.152±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  81
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4,3',4'-tetramethoxy-N-(2-phenylethyl)phenylthioacetamide 在 镍 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 81.0h， 生成 1-[1-[(3,4-二甲氧基苯基)甲基]-6,7-二甲氧基-3,4-二氢-1H-异喹啉-2-基]乙酮
  参考文献：
  名称：

  A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems

  摘要：

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.

  DOI：

  10.1021/jo991742h
• 作为产物：
  描述：

  (3,4-二甲氧基苯基)乙酰氯 在 劳森试剂 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 7.0h， 生成 3,4,3',4'-tetramethoxy-N-(2-phenylethyl)phenylthioacetamide
  参考文献：
  名称：

  A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems

  摘要：

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.

  DOI：

  10.1021/jo991742h

文献信息

• Nakova, E.P.; Tolkachev, O.N.; Evstigneeva, R.P., Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, p. 550 - 555
  作者：Nakova, E.P.、Tolkachev, O.N.、Evstigneeva, R.P.

  DOI：——

  日期：——
• HAKOBA E. P.; TOLKACHEV O. N.; EVSTIGNEEVA R. P., ZH. ORGAN. XIMII, 1981, 17, HO 3, 637-642
  作者：HAKOBA E. P.、 TOLKACHEV O. N.、 EVSTIGNEEVA R. P.

  DOI：——

  日期：——
• A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems
  作者：Albert Padwa、L. Scott Beall、Todd M. Heidelbaugh、Bing Liu、Scott M. Sheehan

  DOI：10.1021/jo991742h

  日期：2000.5.1

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.