3,4,7,8-Diphenanthreno-syn-1,5-diazabicyclo<3.3.0>octa-2,7-diene-4,6-dione

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 3,4,7,8-Diphenanthreno-syn-1,5-diazabicyclo<3.3.0>octa-2,7-diene-4,6-dione
• 英文别名: 3,4,7,8-Diphenanthreno-syn-1,5-diazabicyclo[3.3.0]octa-2,7-diene-4,6-dione；1,17-Diazaoctacyclo[15.15.0.02,15.03,8.09,14.019,32.020,25.026,31]dotriaconta-2(15),3,5,7,9,11,13,19(32),20,22,24,26,28,30-tetradecaene-16,18-dione
• 化学式: C₃₀H₁₆N₂O₂
• 分子量: 436.469
• InChiKey: BHRIORIQUHRPMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  5,7-Bis(diazo)-1,2,3,4-dibenzocyclohepta-1,3-dien-6-one 生成 3,4,7,8-Diphenanthreno-syn-1,5-diazabicyclo<3.3.0>octa-2,7-diene-4,6-dione
  参考文献：
  名称：

  DFT 计算和合成揭示：关键中间体、省略的机制和不对称 Bimane 产品

  摘要：

  我们研究了荧光顺式双烷形成的机制。这项工作结合了理论和实验方法。我们的计算研究支持 Kosower 的机制，同时引入了关键的二氮丙啶中间体。我们的结果表明限速步骤是重氮酮的形成。4,5-二甲基-2,3-二氮杂环戊二烯酮与二苯基环丙烯酮的反应产生了意想不到的不对称反-(Me,Me)(Ph,Ph)bimane。

  DOI：

  10.1002/ejoc.202300697

文献信息

• Synthesis and Photochemistry of 5,7-Bis(diazo)-1,2,3,4-dibenzocyclohepta-1,3-dien-6-one. Generation and Reactions of Phenanthrenodiazacyclopentadiene, Phenanthrenocyclopropenone, and 9,10-Phenanthryne
  作者：Hideo Tomioka、Akemi Okuno、Takehiko Sugiyama、Shigeru Murata

  DOI：10.1021/jo00113a011

  日期：1995.4

  The title compound 15 was prepared as the first 1,3-bis(diazo) ketone incorporated into a seven-membered ring, and its photochemical pathways were investigated not only by product analysis study but also by using matrix isolation spectroscopy. Irradiation of 15 in alcoholic solvents gave 9-(alkoxycarbonyl)phenanthrene 16 as a main product, while similar irradiation in non-nucleophilic solvents provided diphenanthreno-syn-1,5-diazabicyclo[3.3.0]octadienedione (20), The formation of these products is interpreted as indicating that 15 eliminates one of two diazo functions upon photoexcitation to form 9-diazo-10-carbonylphenanthrene (21) which either reacts with alcohol by eliminating the second dinitrogen, leading to 16, or undergoes dimerization to form 20. Photolysis of 15 in an ethanol matrix at 77 K gave 9-ethoxyphenanthrene (31) as a new product along with 16. Irradiation of 15, matrix-isolated in Ar at 10 K monitored by IR, indicated that phenanthrenocyclopropenone (28) was formed as an initial product which then underwent photodecarbonylation to leave 9,10-phenanthryne (32), and that 32 reacted with CO to reproduce 28 upon photoexcitation. The cyclopropenone (28) was shown to be generated also by photolysis of 9,10-dicarboxyphenanthrene anhydride (33) in Ar matrix at 10 K. A plausible mechanism to explain the observed sequential decomposition of the two diazo functions in the room temperature photolytic run and the formal simultaneous elimination of two dinitrogens in the low temperature matrix run is proposed.
• [EN] NITROGENOUS HETEROCYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES<br/>[FR] COMPOSÉS HÉTÉROCYCLIQUES AZOTÉS POUR DISPOSITIFS ÉLECTROLUMINESCENTS ORGANIQUES<br/>[DE] STICKSTOFFHALTIGE, HETEROCYCLISCHE VERBINDUNGEN FÜR ORGANISCHE ELEKTROLUMINESZENZVORRICHTUNGEN
  申请人：[de]MERCK PATENT GMBH

  公开号：WO2022229234A1

  公开（公告）日：2022-11-03

  Die vorliegende Erfindung betrifft stickstoffhaltige, heterocyclische Verbindungen, die sich für die Verwendung in elektronischen Vorrichtungen eignen, sowie elektronische Vorrichtungen, insbesondere organischen Elektrolumineszenzvorrichtungen, enthaltend diese Verbindungen.