(10R,11R,1'S)-10,11-diethyl-5-(1,2,3,4-tetrahydro-1-naphthalenyliden-2'-thirrane)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene | 296801-33-7

• 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,1'S)-10,11-diethyl-5-(1,2,3,4-tetrahydro-1-naphthalenyliden-2'-thirrane)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene
• CAS: 296801-33-7
• 化学式: C₂₉H₃₀S
• 分子量: 410.623
• InChiKey: KORQQJVDDXZYDP-XJGOYTCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (10R,11R,1'S)-10,11-diethyl-5-(1,2,3,4-tetrahydro-1-naphthalenyliden-2'-thirrane)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene 在 铜 作用下， 以 xylene 为溶剂， 反应 2.0h， 以100%的产率得到(10R,11R,P)-10,11-diethyl-5-(1,2,3,4-tetrahydro-1-naphthalenyliden)-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 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 61.0h， 生成 (10R,11R,1'S)-10,11-diethyl-5-(1,2,3,4-tetrahydro-1-naphthalenyliden-2'-thirrane)-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

文献信息

• <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.