avicine-formamide | 94641-60-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: avicine-formamide
• 英文别名: 1-Formamido-1,2,3,4-tetrahydro-6,7-methylendioxy-2-<3,4-methylendioxyphenyl>-naphthalin；N-(6-benzo[1,3]dioxol-5-yl-5,6,7,8-tetrahydro-naphtho[2,3-d][1,3]dioxol-5-yl)-formamide
• CAS: 94641-60-8
• 化学式: C₁₉H₁₇NO₅
• 分子量: 339.348
• InChiKey: SZUGCOQRTFSVAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.66
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  66.02
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  avicine-formamide 在 palladium on activated charcoal 三氯氧磷 作用下， 以 甲苯 为溶剂， 生成 5-methyl[1,3]benzodioxolo[5,6-c][1,3]dioxolo[4,5-j]phenanthridin-6(5H)-one
  参考文献：
  名称：

  Synthesis of oxyavicine

  摘要：

  DOI：

  10.1016/s0040-4020(01)92183-0

文献信息

• Studies on the chemical constituents of rutaceous plants. LIV. The development of a versatile method for the synthesis of antitumor-active benzo(c)phenanthridine alkaloids. 4. Limitation of Bischler-Napieralski cyclization and detailed examination of the dehydrogenation of the Bischler-Napieralski p
  作者：HISASHI ISHII、KENICHI HARADA、TOSHIAKI ISHIDA、TAKEO DEUSHI、TAKESHI MASUDA、MITSUGI SAKAMOTO、YUH-ICHIRO ICHIKAWA、TSUTOMU TAKAHASHI、MUNEKAZU ISHIKAWA、TSUTOMU ISHIKAWA

  DOI：10.1248/cpb.32.2971

  日期：——

  In order to establish a versatile method for the preparation of antiumor benzo [c] phenanthridine alkaloids, the reaction steps from the 2-aryl-1-formamido-1, 2, 3, 4-tetrahydronaphthalenes (2) to the fully aromatized benzo [c] phenanthridine derivatives (5) via the 4b, 10b, 11, 12-tetrahydrobenzo [c] phenanthridines (4) in the Robinson preparative sequence were examined in detail. Bischler-Napieralski reaction of the formamide (2) having an alkoxy group at the para position to the cyclizing point of the 2-phenyl ring substituent gave a mixture of the trans-and cistetrahydrobenzo [c] phenanthridines (4) with or without formation of the 2-aryl-3, 4-dihydronaphthalene derivative (6). There is a limitation in that the presence of the alkoxy group at the para position is required for success in cyclizing the formamide derivative (2). Otherwise, the 2-aryl-3, 4-dihydronaphthalene derivative (6) is the sole product. For the dehydrogenation of the resulting trans-and cis-tetrahydrobenzo [c] phenanthridines (trans-and cis-4) into the fully aromatized product (5), catalytic dehydrogenation with 30% palladium-charcoal in p-cymene and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) oxidation in the presence of or in the absence of 5% sodium hydroxide aqueous solution were investigated. The catalytic dehydrogenation provided either the desired fully aromatized product (5) or the dihydrobenzo [c] phenanthridine (8). The species of the product depends upon the species of the starting material (4). The DDQ-oxidation gave a variety of results. The mode of product formation seems to be regulated by various factors, including the reaction conditions, the species of substituents of the starting material (4), and the stereochemistry of the starting material (4). The mechanisms of formation of various products are discussed.

  为了建立一种制备抗肿瘤苯并[c]菲啶生物碱的多功能方法，我们详细研究了从 2-芳基-1-甲酰氨基-1，2，3，4-四氢萘 (2) 到完全芳香化的苯并[c]菲啶衍生物 (5)，经由 4b，10b，11，12-四氢苯并[c]菲啶 (4) 的反应步骤。对位上有烷氧基的甲酰胺（2）与 2-苯基环取代基的环化点发生 Bischler-Napieralski 反应，生成了反式和双四氢苯并[c]菲啶（4）的混合物，无论是否形成 2-芳基-3，4-二氢萘衍生物（6）。环化甲酰胺衍生物（2）有一个局限性，即需要在对位存在烷氧基。否则，2-芳基-3，4-二氢萘衍生物（6）是唯一的产物。为了将生成的反式和顺式四氢苯并[c]菲啶（反式和顺式-4）脱氢为完全芳香化的产物（5），研究了在有或没有 5%氢氧化钠水溶液的情况下，在对甲苯和 2，3-二氯-5，6-二氰基-1，4-苯醌（DDQ）氧化中使用 30%钯炭进行催化脱氢。催化脱氢反应提供了所需的完全芳香化产物（5）或二氢苯并 [c] 菲啶（8）。产物的种类取决于起始物质（4）的种类。DDQ 氧化反应产生了多种结果。产物的形成方式似乎受多种因素的制约，包括反应条件、起始物质的取代基种类 (4) 和起始物质的立体化学结构 (4)。本文讨论了各种产物的形成机理。