(10R,11R)-10,11-diethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-thione | 296801-32-6

• 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: (10R,11R)-10,11-diethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-thione
• 英文别名: (9R,10R)-9,10-diethyltricyclo[9.4.0.03,8]pentadeca-1(15),3,5,7,11,13-hexaene-2-thione
• CAS: 296801-32-6
• 化学式: C₁₉H₂₀S
• 分子量: 280.434
• InChiKey: NXZJYCMWMAZIPJ-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (10R,11R)-10,11-diethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-thione 在 铜 作用下， 以 二氯甲烷 、 xylene 为溶剂， 反应 18.0h， 生成 (10R,11R,P)-10,11-diethyl-5-(1,2,3,4-tetrahydro-4-phenanthrenyliden)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene
  参考文献：
  名称：

  C₂-Symmetric Dibenzosuberane-Based Helicenes as Potential Chirochromic Optical Switches

  摘要：

  Three C-2-symmetric (10R,11R)-diethyl substituted dibenzosuberane (DBS)-based helicenes with varying steric and conjugation demands of their bottom fragments were synthesized. The X-ray analyses of their precursors-episulfides reveal the preferred conformation of the DBS skeleton possessing equatorially oriented ethyl groups at C-8 and C-9 positions. In all cases, the absolute configuration in the episulfide moiety is S, which can lead stereospecifically to the corresponding P helicenes after the reductive desulfurization of the episulfides. Only the helicene 7a with the bottom part derived from alpha-tetralone was found photoswitchable in reasonable time scale. Photoisomerization of the diastereomerically pure (10R,11R,P)-helicene (7a) at 280 nm led to virtually exclusive formation of the opposite M form-diastereomer 7a' (7a'/7a = 99.6/0.4). The preferential return of 7a' to 7a can be effected upon irradiation at 254 nm (7a'/7a = 33/67) or thermally at 130 degrees C (7a'/7a = 0/100). The photoinduced switching process amounts to a 133% difference in de (from 99.2% to -34%). The concomitant change of helicene chirality between these two diastereomeric photostationary states augurs well for their potential application as an optical switch in LC materials. To our knowledge, our system serves as the best chirochromic optical switch as compared to the examples possessing similar photochromic properties.

  DOI：

  10.1021/ja993297d
• 作为产物：
  描述：

  (10R,11R)-11-(({[(4-methylphenyl)sulfonyl]oxy}methyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-10-yl)methyl 4-methyl-1-benzenesulfonate 在 二环己烷并-18-冠醚-6 、 potassium permanganate 、 copper(l) iodide 、 tetraphosphorus decasulfide 作用下， 以 乙醚 、 甲苯 、 苯 为溶剂， 反应 45.0h， 生成 (10R,11R)-10,11-diethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-thione
  参考文献：
  名称：

  C₂-Symmetric Dibenzosuberane-Based Helicenes as Potential Chirochromic Optical Switches

  摘要：

  Three C-2-symmetric (10R,11R)-diethyl substituted dibenzosuberane (DBS)-based helicenes with varying steric and conjugation demands of their bottom fragments were synthesized. The X-ray analyses of their precursors-episulfides reveal the preferred conformation of the DBS skeleton possessing equatorially oriented ethyl groups at C-8 and C-9 positions. In all cases, the absolute configuration in the episulfide moiety is S, which can lead stereospecifically to the corresponding P helicenes after the reductive desulfurization of the episulfides. Only the helicene 7a with the bottom part derived from alpha-tetralone was found photoswitchable in reasonable time scale. Photoisomerization of the diastereomerically pure (10R,11R,P)-helicene (7a) at 280 nm led to virtually exclusive formation of the opposite M form-diastereomer 7a' (7a'/7a = 99.6/0.4). The preferential return of 7a' to 7a can be effected upon irradiation at 254 nm (7a'/7a = 33/67) or thermally at 130 degrees C (7a'/7a = 0/100). The photoinduced switching process amounts to a 133% difference in de (from 99.2% to -34%). The concomitant change of helicene chirality between these two diastereomeric photostationary states augurs well for their potential application as an optical switch in LC materials. To our knowledge, our system serves as the best chirochromic optical switch as compared to the examples possessing similar photochromic properties.

  DOI：

  10.1021/ja993297d

文献信息

• Modulation of Photoswitching Profiles by 10,11-Dialkoxymethyl Substituents in C2-Symmetric Dibenzosuberane-Based Helicenes
  作者：Wen-Ching Chen、Po-Chiao Lin、Chien-Hsiang Chen、Chien-Tien Chen

  DOI：10.1002/chem.201002123

  日期：2010.11.15

  A series of C2‐symmetric, 10,11‐disubstituted dibenzosuberane (DBS)‐based helicenes 6 a–c with a common 7‐bromo‐α‐tetralin‐based bottom fragment were synthesized. Their absolute stereochemistry was determined to be 10R,11R,P after reductive desulfurization of the corresponding (10R,11R,1′S)‐episulfides with complete stereospecificity. Photoisomerization of the diastereomerically pure (P)‐6 c in hexane

  合成了一系列基于C 2对称的10,11-二取代的二苯并亚戊二烷（DBS）的螺旋烯6 a – c，具有一个常见的基于7溴α-四氢萘的底部片段。相应的（10 R，11 R，1 'S）-环硫化物经过还原性脱硫后，其绝对立体化学确定为10 R，11 R，P，具有完全的立体特异性。非对映体纯（P）-6 c在己烷中的光异构化导致相反的M形非对映体（P / M'，<1：> 99）在290 nm。在330 nm处具有高选择性（P / M'，90:10）的情况下，（M'）- 6 c优先返回（P）-6 c也实现了优先返回。（P）-6 c和（M'）- 6 c都具有两个DBS构象的分子模拟表明，光开关的选择性由顶部DBS模板的构象控制，如其1 H NMR光谱所证明的。将6 c掺杂到向列液晶（E7）中导致胆甾型中间相具有调制的螺距，可逆的螺旋感和三元逻辑的开关存储器。
• <i>C</i>₂-Symmetric Dibenzosuberane-Based Helicenes as Potential Chirochromic Optical Switches
  作者：Chien-Tien Chen、Y-Chen Chou

  DOI：10.1021/ja993297d

  日期：2000.8.1

  Three C-2-symmetric (10R,11R)-diethyl substituted dibenzosuberane (DBS)-based helicenes with varying steric and conjugation demands of their bottom fragments were synthesized. The X-ray analyses of their precursors-episulfides reveal the preferred conformation of the DBS skeleton possessing equatorially oriented ethyl groups at C-8 and C-9 positions. In all cases, the absolute configuration in the episulfide moiety is S, which can lead stereospecifically to the corresponding P helicenes after the reductive desulfurization of the episulfides. Only the helicene 7a with the bottom part derived from alpha-tetralone was found photoswitchable in reasonable time scale. Photoisomerization of the diastereomerically pure (10R,11R,P)-helicene (7a) at 280 nm led to virtually exclusive formation of the opposite M form-diastereomer 7a' (7a'/7a = 99.6/0.4). The preferential return of 7a' to 7a can be effected upon irradiation at 254 nm (7a'/7a = 33/67) or thermally at 130 degrees C (7a'/7a = 0/100). The photoinduced switching process amounts to a 133% difference in de (from 99.2% to -34%). The concomitant change of helicene chirality between these two diastereomeric photostationary states augurs well for their potential application as an optical switch in LC materials. To our knowledge, our system serves as the best chirochromic optical switch as compared to the examples possessing similar photochromic properties.