2',3',2'',3''-tetramethoxy-2,3:6,7-dibenzo-9-oxabicyclo<3.3.1>nona-2,6-diene | 77733-40-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2',3',2'',3''-tetramethoxy-2,3:6,7-dibenzo-9-oxabicyclo<3.3.1>nona-2,6-diene
• 英文别名: 2,3,8,9-tetramethoxy-5,6,11,12-tetrahydro-5,11-epoxydibenzo[a,e][8]annulene；2’,3’,2”,3”-tetramethoxy-2,3:6,7-dibenzo-9-oxabicyclo[3.3.1]nona-2,6-diene；4,5,12,13-Tetramethoxy-17-oxatetracyclo[7.7.1.02,7.010,15]heptadeca-2,4,6,10,12,14-hexaene
• CAS: 77733-40-5
• 化学式: C₂₀H₂₂O₅
• 分子量: 342.392
• InChiKey: BSTRZFRADQWXKM-UHFFFAOYSA-N

物化性质

• 熔点：
  162-164 °C
• 沸点：
  457.3±45.0 °C(Predicted)
• 密度：
  1.191±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2',3',2'',3''-tetramethoxy-2,3:6,7-dibenzo-9-oxabicyclo<3.3.1>nona-2,6-diene 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以95%的产率得到5,6-Dihydrodibenzocyclooctene-5-ol
  参考文献：
  名称：

  手性旋光的Buta-1,3-二烯的应变加速形成

  摘要：

  研究了四氰基乙烯（TCNE）与应变的，富电子的二苯并稠合的环辛炔之间的正式[2 + 2]环加成-逆电环化（CA-RE）反应。定量了环应变对反应动力学的影响，表明使用应变的环状炔烃在298 K时的环加成速率比使用未应变的炔烃的环加成速率高5500倍。分离了环丁烯反应中间体以及1,3-二烯丁二烯产物，并对其晶体结构进行了结晶学研究。据报道，有一个罕见的手性丁1，3-二烯在室温下具有光学活性和构型稳定性的例子被分离出来。关于buta-1对映异构化途径的计算研究，3-二烯产品显示，八元环通过翻盖机制中的舟形变矩器反转。与计算值一致，发现这些化合物中通过实验测得的外消旋化激活障碍高达26 kcal mol-1。

  DOI：

  10.1002/anie.201409289
• 作为产物：
  描述：

  5,6-Dihydrodibenzocyclooctene-5-ol 在 sodium hydroxide 、 sodium tetrahydroborate 、 mercury(II) diacetate 作用下， 生成 2',3',2'',3''-tetramethoxy-2,3:6,7-dibenzo-9-oxabicyclo<3.3.1>nona-2,6-diene
  参考文献：
  名称：

  Total synthesis of isopavine and intermediates for the preparation of substituted amitriptyline analogs: facile routes to substituted dibenzocyclooctatrienes and dibenzocycloheptatrienes

  摘要：

  DOI：

  10.1021/ja00398a019

文献信息

• Facile access to methoxylated 2-phenylnaphthalenes and epoxydibenzocyclooctenes
  作者：Cédric Maurin、Fabrice Bailly、Philippe Cotelle

  DOI：10.1016/j.tet.2005.02.091

  日期：2005.7

  were treated with concentrated hydrochloric acid in 1,4-dioxane to give methoxylated 2-phenylnaphthalenes or 1,2,9,10-tetrahydro-1,9-epoxydibenzo[a,e]cyclooctenes. Yields in 2-phenylnaphthalenes were quite good and 1,2,9,10-tetrahydro-1,9-epoxydibenzo[a,e]cyclooctenes could be easily isolated. 2-Phenylnaphthalenes were obtained by a tandem aldol condensation-intramolecular Friedel–Crafts cyclisation

  在浓盐酸中在1,4-二恶烷中处理甲氧基化的苯乙醛，得到甲氧基化的2-苯基萘或1,2,9,10-四氢-1,9-环氧二苯并[ a，e ]环辛烯。2-苯基萘的收率相当好，并且可以容易地分离出1,2,9,10-四氢-1,9-环氧二苯并[ a，e ]环辛烯。通过串联的羟醛缩合-分子内Friedel-Crafts环化和1,2,9,10-四氢-1,9-环氧二苯并[ a，e ]环辛烯通过O缩合然后再进行两次分子内的Friedel-化，获得2-苯基萘。工艺品烷基化。
• Dibenzocyclooctendiones (DBCDOs): Arginine-Selective Chemical Labeling Reagents Obtained through Benzilic Acid Rearrangement
  作者：Cheng-Ting Shih、Bo-Hong Kuo、Chun-Yi Tsai、Mei-Chun Tseng、Jiun-Jie Shie

  DOI：10.1021/acs.orglett.2c01970

  日期：2022.7.1

  dibenzocyclooctendiones (DBCDOs) are efficient chemical reagents for the site-specific labeling of arginine-containing biomolecules. Unlike the commonly used probes, DBCDOs undergo an irreversible ring-contracted rearrangement with the guanidinium group on arginine residues under mild reaction conditions. The regioselective dual-labeled arginine residues were obtained in a one-pot reaction with our tested

  我们证明二苯并环辛二酮 (DBCDO) 是用于对含精氨酸的生物分子进行位点特异性标记的有效化学试剂。与常用的探针不同，DBCDO 在温和的反应条件下与精氨酸残基上的胍基团发生不可逆的缩环重排。区域选择性双标记精氨酸残基是在与我们测试的底物的一锅反应中获得的。DBCDOs 反应的效率及其易于合成使 DBCDOs 成为精氨酸位点选择性生物共轭的有吸引力的选择。
• Synthesis of Tetra(2-hydroxyethoxy)-Substituted Dibenzocyclooctyne Derivatives as Novel, Highly Hydrophilic Tool Compounds for Strain-Promoted Alkyne-Azide Cycloaddition Applications
  作者：Martin Golkowski、Thomas Ziegler

  DOI：10.1055/s-0032-1316875

  日期：——

  The synthesis of a novel, hydrophilic dibenzocyclooctyne derivative for strain-promoted alkyne-azide cycloaddition (SPAAC) is described. Starting from 2-(3,4-dimethoxyphenyl)acetaldehyde, the corresponding activated carbonate of 2,3,8,9-tetrakis(2-hydroxyethoxy)-5,6-dihydro-11,12-didehydrodibenzo[a,e][8]annulene, termed THE-DIBO, was prepared in seven steps and 24% overall yield. A water-soluble THE-DIBO analogue showed a k(2) value of (21.9 +/- 0.2) x 10(-2) M-1 s(-1) for SPAAC with 2-azidoethanol in water. The high hydrophilicity and steric bulk of THE-DIBO derivatives should to suppress nonspecific thiol-yne addition of proteins to strained alkynes observed for SPAAC labeling in complex proteomes.
• High Spatiotemporal Control of Spontaneous Reactions Using Ultrasound-Triggered Composite Droplets
  作者：Marine Bezagu、Claudia Errico、Victor Chaulot-Talmon、Fabrice Monti、Mickael Tanter、Patrick Tabeling、Janine Cossy、Stellios Arseniyadis、Olivier Couture

  DOI：10.1021/ja5019354

  日期：2014.5.21

  Achieving high spatial and temporal control over a spontaneous reaction is a particularly challenging task with potential breakthroughs in various fields of research including surface patterning and drug delivery. We report here an exceptionally effective method that allows attaining such control. This method relies on a remotely triggered ultrasound-induced release of a reactant encapsulated in a composite microdroplet of liquid perfluorohexane. More specifically, the demonstration was achieved by locally applying a focused 2.25 MHz transducer onto a microfluidic channel in which were injected composite microdroplets containing a solution of an azidocoumarin and an external flow containing a reactive alkyne.
• 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