(-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11-dimethyldibenzo[c,e]thiepine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并硫平类
• 英文名称: (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11-dimethyldibenzo[c,e]thiepine
• 英文别名: [3-(4-Dodecoxybenzoyl)oxy-1,11-dimethyl-5,7-dihydrobenzo[d][2]benzothiepin-9-yl] 4-dodecoxybenzoate
• 化学式: C₅₄H₇₂O₆S
• 分子量: 849.228
• InChiKey: ADXJEFPBKUVKET-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.2
• 重原子数：
  61
• 可旋转键数：
  30
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  96.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11-dimethyldibenzo[c,e]thiepine 在 N-methyl-1,2-epoxy-1,2,3,4-tetrahydroisoquinolinium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以96%的产率得到(-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11-dimethyldibenzo[c,e]thiepin dioxide
  参考文献：
  名称：

  A New Family of Enantiomerically Pure Smectic C* Liquid Crystals with a Bridged Chiral Biphenyl Core

  摘要：

  The synthesis of enantiomerically pure bridged biphenyl compounds, (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1, 11-dimethyldibenzo[c,e]thiepine, 13, and (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11 dioxide, 14, is described. This is the first report of smectic C* mesophases with a rigid twisted biphenyl core and axial chirality.

  DOI：

  10.1021/jo972143i
• 作为产物：
  描述：

  (2-bromo-5-methoxy-3-methylphenyl)methanol 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 potassium permanganate 、 lithium aluminium tetrahydride 、 三甲基氯硅烷 、 氯化亚砜 、 草酰氯 、 lithium sulfide 、 水 、 三溴化硼 、 铜 、 二甲基亚砜 、 sodium sulfate 、 三乙胺 、 三氟乙酸 、 sodium iodide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 、 苯 为溶剂， 反应 107.83h， 生成 (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11-dimethyldibenzo[c,e]thiepine
  参考文献：
  名称：

  A New Family of Enantiomerically Pure Smectic C* Liquid Crystals with a Bridged Chiral Biphenyl Core

  摘要：

  The synthesis of enantiomerically pure bridged biphenyl compounds, (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1, 11-dimethyldibenzo[c,e]thiepine, 13, and (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11 dioxide, 14, is described. This is the first report of smectic C* mesophases with a rigid twisted biphenyl core and axial chirality.

  DOI：

  10.1021/jo972143i

文献信息

• Chiral induction in nematic and smectic C liquid crystal phases by dopants with axially chiral 1,11-dimethyl-5,7-dihydrodibenz[c,e]thiepin cores
  作者：Matthew P. Thompson、Robert P. Lemieux

  DOI：10.1039/b712253e

  日期：——

  Three calamitic molecules with axially chiral cores, (S)-3,9-bis[(4-dodecyloxybenzoyl)oxy]-1,11-dimethyl-5,7-dihydrodibenzo[c,e]thiepin (5a), (R)-3,9-bis[(4-butoxybenzoyl)oxy]-1,11-dimethyl-5,7-dihydrodibenzo[c,e]thiepin (5b), and (R)-3,9-bis[(4-octyloxybenzoyl)oxy]-1,11-dimethyl-5,7-dihydrodibenzo[c,e]thiepin (5c), were synthesized in optically pure form and doped in four calamitic liquid crystal hosts with I–N–SmA–SmC (INAC) phase sequences (PhP, PhB, NCB76 and DFT), and in the nematic host 5CB. Helical twisting powers (β) in the N* phase are in the range of 24–43 µm–1 with the INAC hosts, and in the range of 56–58 µm–1 with 5CB at T–TN-I = –2 K, which are comparable to those previously reported for axially chiral binaphthyls. Interestingly, these dopants were found to stabilize and broaden the temperature range of the N* phase in 5CB. With some of the dopant–INAC host mixtures, the induction of a chiral TGBA* phase was also observed. Dopant 5a induces a measurable spontaneous polarization in the SmC phase of the achiral phenylpyrimidine host PhP, giving a polarization power δp of –104 ± 20 nC cm–2. Comparisons of helical twisting powers in the N* and SmC* phases, and polarization powers in the SmC* phase, for dopants 5a–c and the dinitro analogue (+)-1,11-dinitro-3,9-bis[(4-nonyloxybenzoyl)oxy]-5,7-dihydrodibenzo[c,e]thiepin (4) suggest that the nitro substituents play a dominant role in promoting chirality transfer in the SmC* phase, whereas the helical topography of the core appears to be a more important factor in promoting chirality transfer in the N* phase.

  三种具有轴向手性核心的钙钛矿分子：(S)-3,9-双[(4-十二烷氧基苯甲酰基)氧基]-1,11-二甲基-5,7-二氢二苯并[c,e]硫杂卓(5a)、(R)-3,9-双[(4-丁氧基苯甲酰基)氧基]-1,11-二甲基-5,7-二氢二苯并[c,e]硫杂卓 (5b)，以及 (R)-3,9-双[(4-辛氧基苯甲酰基)氧基]-1、11-二甲基-5,7-二氢二苯并[c,e]硫杂卓 (5c) 的光学纯品，并掺杂在具有 I-N-SmA-SmC (INAC) 相序的四种钙钛矿液晶宿主（PhP、PhB、NCB76 和 DFT）以及向列宿主 5CB 中。在 T-TN-I = -2 K 时，INAC 主晶在 N* 相中的螺旋扭转力 (β)范围为 24-43 µm-1，5CB 为 56-58 µm-1，与之前报道的轴向手性双萘的螺旋扭转力相当。有趣的是，这些掺杂剂能稳定和拓宽 5CB 中 N* 相的温度范围。在某些掺杂剂-INAC 主混合物中，还观察到诱导出了手性 TGBA* 相。掺杂剂 5a 可诱导非手性苯基嘧啶宿主 PhP 的 SmC 相产生可测量的自发极化，极化功率 δp 为 -104 ± 20 nC cm-2。比较了掺杂剂 5a-c 和二硝基类似物 (+)-1,11- 二硝基-3,9-双[(4-壬氧基苯甲酰基)氧基]-5,7-二氢二苯并[c、e]硫杂卓 (4) 表明，硝基取代基在促进 SmC* 相手性转移方面起着主导作用，而核心的螺旋形貌似乎是促进 N* 相手性转移的更重要因素。
• A New Family of Enantiomerically Pure Smectic C* Liquid Crystals with a Bridged Chiral Biphenyl Core
  作者：Guy Solladié、Philippe Hugelé、Richard Bartsch

  DOI：10.1021/jo972143i

  日期：1998.6.1

  The synthesis of enantiomerically pure bridged biphenyl compounds, (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1, 11-dimethyldibenzo[c,e]thiepine, 13, and (-)-(R)-3,9-bis(4-(dodecyloxy)benzoyloxy)-5,7-dihydro-1,11 dioxide, 14, is described. This is the first report of smectic C* mesophases with a rigid twisted biphenyl core and axial chirality.