2,3,7,8-tetramethoxy-10,11-dihydro-5H-10,5-azaethano-dibenzo[a,d]cycloheptene | 68907-92-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 二苯并环庚烯
• 英文名称: 2,3,7,8-tetramethoxy-10,11-dihydro-5H-10,5-azaethano-dibenzo[a,d]cycloheptene
• 英文别名: 2,3,7,8-Tetramethoxy-10,11-dihydro-5H-10,5-azaaethano-dibenzo[a,d]cyclohepten；Isopavine；4,5,12,13-tetramethoxy-17-azatetracyclo[7.6.2.02,7.010,15]heptadeca-2,4,6,10,12,14-hexaene
• CAS: 68907-92-6
• 化学式: C₂₀H₂₃NO₄
• 分子量: 341.407
• InChiKey: ZNIIISXAGSAJQE-UHFFFAOYSA-N

物化性质

• 沸点：
  467.2±45.0 °C(Predicted)
• 密度：
  1.167±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  49
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3,7,8-tetramethoxy-10,11-dihydro-5H-10,5-azaethano-dibenzo[a,d]cycloheptene 在 氢氧化钾 、 potassium permanganate 作用下， 生成 2,3,6,7-四甲氧基蒽醌 、 2,3,7,8-tetramethoxy-5,10-dihydro-10,5-azaethano-dibenzo[a,d]cycloheptene-11,13-dione
  参考文献：
  名称：

  Waldmann; Chwala, Justus Liebigs Annalen der Chemie, 1957, vol. 609, p. 125,141

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2-bis(3,4-dimethoxyphenyl)ethanone 在 盐酸 、 1,2,3,4-四氢萘 、 phosphorus pentoxide 、 potassium carbonate 作用下， 生成 2,3,7,8-tetramethoxy-10,11-dihydro-5H-10,5-azaethano-dibenzo[a,d]cycloheptene
  参考文献：
  名称：

  Waldmann; Chwala, Justus Liebigs Annalen der Chemie, 1957, vol. 609, p. 125,141

  摘要：

  DOI：

文献信息

• STUDIES IN THE POLYOXYPHENOL SERIES: IX. THE SYNTHESIS OF PAPAVERINE AND PAPAVERALDINE BY THE POMERANZ-FRITSCH METHOD
  作者：Donald A. Guthrie、Arlen W. Frank、C. B. Purves

  DOI：10.1139/v55-090

  日期：1955.5.1

  Fritsch's cyclization of N-(α-veratrylveratrylidene)-aminoacetal in sulphuric acid was shown to give 1.1% of papaverine and 23% of an isomer, m.p. 164.5–165.5 °C.; hydrochloride, m.p. 212 °C. decomp., which was supposed to be 4,5-bis(3,4-dimethoxyphenyl)-2H-pyrrolenine, produced by an internal condensation of the acetal or the corresponding aldehyde with the reactive methylene group. A similar structure was proposed for another unidentified isomer prepared by Schlittler and Müller. Hydrogenation of Fritsch's acetal gave N-(α-veratryl-veratryl)-aminoacetal, m.p. 69.5–70 °C., which was cyclized to a base, m.p. 155.5–156 °C.; N-acetyl derivative, m.p. 203.5–204 °C., formulated as 2,3-bis(3,4-dimethoxyphenyl)-3-pyrroline. Substances presumed to be the intermediate aldehyde and aldol were isolated as colorless oils. Condensation of the diketone veratril with aminoacetal, followed by cyclization of the crude product, constituted a new two-step synthesis of papaveraldine in 8% yield, and the reduction of the latter to papaverine was known.Other crystalline compounds prepared incidentally and thought to be new were veratril monoanil, m.p. 172–173 °C.; α,α′-biveratrylideneaminoacetal, m.p. 101–102 °C.; a compound formulated as 2,3-bis(3,4-dimethoxyphenyl)-4-ethylmer-captopyrrolidine hydrochloride, m.p. 184–185 °C; from this an unidentified mercury complex, m.p. 109 °C. decomp.; 4,4′dibenzyloxy-3,3′-dimethoxy-desoxybenzoin, m.p. 141–142 °C; and its oxime, m.p. 137.5 °C.

  Fritsch在硫酸中对N-(α-芍药碱基芍药碱亚甲基)-氨基乙醛进行环化反应，结果显示产率为1.1%的罂粟碱和23%的异构体，熔点为164.5–165.5°C；盐酸盐，熔点为212°C分解。这种异构体被认为是4,5-双(3,4-二甲氧基苯基)-2H-吡咯烯，通过乙醛或相应醛与活性甲基的内部缩合产生。 Schlittler和Müller制备的另一种未知异构体也提出了类似的结构。Fritsch的亚甲基环化反应产生了N-(α-芍药碱基芍药碱)-氨基乙醛，熔点为69.5–70°C，它被环化成一种碱，熔点为155.5–156°C；N-乙酰衍生物，熔点为203.5–204°C，被确定为2,3-双(3,4-二甲氧基苯基)-3-吡咯烯。假定为中间醛和醛缩合物的物质被分离为无色油状物。芍药碱的新的两步合成方法包括芍药碱基芍药碱与氨基乙醛的缩合，随后对粗产品进行环化反应，产率为8%。将后者还原为罂粟碱是已知的。其他结晶化合物包括芍药碱基单苯胺，熔点为172–173°C；α,α′-双(芍药碱基)-氨基乙醛，熔点为101–102°C；一种被确定为2,3-双(3,4-二甲氧基苯基)-4-乙基巯基吡咯啉盐酸盐的化合物，熔点为184–185°C；从中得到的未知汞络合物，熔点为109°C分解；4,4′-二苄氧基-3,3′-二甲氧基-去氧苯酮，熔点为141–142°C；以及它的肟，熔点为137.5°C。
• Formation of isopavine by the cyclization of N-(.ALPHA.-(3,4-dimethoxybenzyl)-3,4-dimethoxybenzyl)aminoacetal with chlorosulfonic acid.
  作者：KAZUKO KIDO、YASUO WATANABE

  DOI：10.1248/cpb.29.861

  日期：——

  Treatment of N-[α-(3, 4-dimethoxybenzyl)-3, 4-dimethoxybenzyl] aminoacetal (1) or its oxalate with chlorosulfonic acid at low temperature gave isopavine (3) in extremely good yield.

  在低温下用氯磺酸处理 N-[α-(3, 4-二甲氧基苄基)-3, 4-二甲氧基苄基]氨基乙缩醛（1）或其草酸盐，可以得到产量极高的异巴维因（3）。
• A Simple and Efficient Synthetic Route to Chiral Isopavines. Synthesis of (−)-<i>O</i>-Methylthalisopavine and (−)-Amurensinine
  作者：Luisa Carrillo、Dolores Badía、Esther Domínguez、José L. Vicario、Imanol Tellitu

  DOI：10.1021/jo9708102

  日期：1997.10.1

  The isopavinan alkaloids (-)-O-methylthalisopavine (7a) and (-)-amurensinine (7d) have been synthesized in good yield and high ee from the appropriate 1,2-diarylethylamine derivatives using optically active beta-amino alcohols as chiral support. This synthetic route employs as key steps the alkylation reaction of the azomethine derivatives 2 with Grignard reagents 1 and a novel one-pot double-intramolecular cyclization of the adequately functionalized 1,2-diarylethylamines 5 to afford a series of optically active isopavines 6a-d and 7a-d.
• 405. Pavine. Part II. The structure of isopavine
  作者：A. R. Battersby、D. A. Yeowell

  DOI：10.1039/jr9580001988

  日期：——
• Total synthesis of isopavine and intermediates for the preparation of substituted amitriptyline analogs: facile routes to substituted dibenzocyclooctatrienes and dibenzocycloheptatrienes
  作者：Michael E. Jung、Steven J. Miller

  DOI：10.1021/ja00398a019

  日期：1981.4