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 | 31537-71-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 中文名称: 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
• 英文名称: N-acetyltetrahydropapaveroline
• 英文别名: N-acetylnorlaudanosine；2-acetyl-1-(3,4-dimethoxy-benzyl)-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline；2-acetyl-1-[(3,4-dimethoxyphenyl)methyl]-1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline；N-Acetyl-tetrahydropapaverin；N-Acetyl-laudanosin；2-Acetyl-1-((3,4-dimethoxyphenyl)methyl)-1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline；1-[1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl]ethanone
• CAS: 31537-71-0
• 化学式: C₂₂H₂₇NO₅
• 分子量: 385.46
• InChiKey: JIDKUPJJVWNDTF-UHFFFAOYSA-N

物化性质

• 沸点：
  548.5±50.0 °C(Predicted)
• 密度：
  1.157±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  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 在 三氟化硼乙醚 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以70%的产率得到(+/-)-7-acetyl-6,7,7a,8-tetrahydro-3,10,11-trimethoxy-dibenz[d,f]indol-2(5H)-one
  参考文献：
  名称：

  通过一锅BischlerNapieralski反应和高价碘试剂的氧化偶联反应合成（±）-甘氨酸和（±）-新螺二烯酮

  摘要：

  3,4- dimethoxybenzeneethanamine（缩合3D）和各种酸苯乙酸，即，图4a - ë，经由一个实用，高效的一锅煮施勒-纳皮耶拉尔斯基反应，随后加入NaBH 4还原，产生了一系列的1-苄基1， 2,3,4-四氢异喹啉，即，图5a - ê，在令人满意的产率（方案3）。后者的N-酰基和N-甲基衍生物6a – e与高价碘（[IPh（CF 3 COO）2 ]）产生具有两个不同骨架的产物（方案4）。N-酰基衍生物6a - c的主要产物为（±）-N-酰基亚螺二酮2a - c，次要产物为3,4-二氢异喹啉7。然而，（±）-甘氨酸（1）是从N-甲基衍生物6e开始的主要产物。提出了用于形成这两种类型骨架的可能的反应机理（方案5）。

  DOI：

  10.1002/hlca.200490005
• 作为产物：
  描述：

  3,4-二甲氧基苯乙酸 在 镍 劳森试剂 、 草酰氯 、 N,N-二甲基甲酰胺 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 90.0h， 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

文献信息

• Photochemically induced cyclization of N-[2-(o-styryl)phenylethyl]acetamides and 5-styryl-1-methyl-1,2,3,4-tetrahydroisoquinolines: new total syntheses of 1-methyl-1,2,3,4-tetrahydronaphtho[2,1-f]isoquinolines
  作者：Elena Martı́nez、Juan C Estévez、Ramón J Estévez、Luis Castedo

  DOI：10.1016/s0040-4020(01)00041-2

  日期：2001.3

  Two new total syntheses of 1-methyl-1,2,3,4-dihydronaphtho[1,2-f]isoquinolines are based on the construction of their phenanthrene ring system by photochemically induced cyclization of N-2-[(E)-2-phenyl-1-ethenyl]phenylethyl}acetamides or 1-methyl-5-[(E)-2-phenyl-1-ethenyl]-1,2,3,4-tetrahydroisoquinolines.

  1-甲基-1,2,3,4-二氢萘并[1,2- f ]异喹啉的两个新的总合成是基于通过光化学诱导的N- 2-[（E） -2-苯基-1-乙烯基]苯基乙基}乙酰胺或1-甲基-5-[（E）-2-苯基-1-乙烯基] -1，2，3，4-四氢异喹啉。
• Illicit heroin manufacturing by-products: capillary gas chromatographic determination and structural elucidation of narcotine- and norlaudanosine-related compounds
  作者：Andrew C. Allen、Donald A. Cooper、James M. Moore、Manfred. Gloger、Helmut. Neumann

  DOI：10.1021/ac00278a072

  日期：1984.12.1
• NOYORI, RYOJI;KITAMURA, MASATO;TAKAYA, HIDEMASA;KUMOBAYASHI, HIDENORI;AKU+
  作者：NOYORI, RYOJI、KITAMURA, MASATO、TAKAYA, HIDEMASA、KUMOBAYASHI, HIDENORI、AKU+

  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.
• Synthesis of (±)-Glaucine and (±)-Neospirodienonevia an One-PotBischlerNapieralski Reaction and Oxidative Coupling by a Hypervalent Iodine Reagent
  作者：Wei-Jan Huang、Om V. Singh、Chung-Hsiung Chen、Shoei-Sheng Lee

  DOI：10.1002/hlca.200490005

  日期：2004.1

  acids, i.e., 4a–e, via a practical and efficient one-pot Bischler–Napieralski reaction, followed by NaBH4 reduction, produced a series of 1-benzyl-1,2,3,4-tetrahydroisoquinolines, i.e., 5a–e, in satisfactory yields (Scheme 3). Oxidative coupling of the N-acyl and N-methyl derivatives 6a–e of the latter with hypervalent iodine ([IPh(CF3COO)2]) yielded products with two different skeletons (Scheme 4). The

  3,4- dimethoxybenzeneethanamine（缩合3D）和各种酸苯乙酸，即，图4a - ë，经由一个实用，高效的一锅煮施勒-纳皮耶拉尔斯基反应，随后加入NaBH 4还原，产生了一系列的1-苄基1， 2,3,4-四氢异喹啉，即，图5a - ê，在令人满意的产率（方案3）。后者的N-酰基和N-甲基衍生物6a – e与高价碘（[IPh（CF 3 COO）2 ]）产生具有两个不同骨架的产物（方案4）。N-酰基衍生物6a - c的主要产物为（±）-N-酰基亚螺二酮2a - c，次要产物为3,4-二氢异喹啉7。然而，（±）-甘氨酸（1）是从N-甲基衍生物6e开始的主要产物。提出了用于形成这两种类型骨架的可能的反应机理（方案5）。