helicenebisquinone | 321961-81-3

• 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: helicenebisquinone
• 英文别名: 6,8,9,11-tetradodecoxyhexahelicene-1,4,13,16-tetrone
• CAS: 321961-81-3；175446-41-0；175524-18-2；217460-34-9
• 化学式: C₇₄H₁₀₈O₈
• 分子量: 1125.67
• InChiKey: VVVACLLCXLXYQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.9
• 重原子数：
  82
• 可旋转键数：
  48
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  helicenebisquinone 在 sodium dithionite 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  共轭螺旋分子的合成与聚集

  摘要：

  描述了合成螺旋双醌1的改进方法和通过分离衍生的莰酸酯来分离其对映体和其他螺旋双醌的对映体的有效方法。对苯醌与 2,7-二乙酰-4,5-二烷氧基萘的双（三异丙基甲硅烷醇醚）结合以 56% 的产率得到螺旋骨架。当十二烷溶液浓缩到 5 × 10-4 M 或更多时，非外消旋 1 的分子会聚集。氯仿分解聚集体。聚集的特征在于增强的圆二色性和 g 值、红移的 UV-vis 吸收、增加的比旋光度、增加吸收频率下的光散射，以及如前所述，转移到红色的荧光发射，1H NMR 共振转移高场，并将纯材料组织成纤维。旋涂薄膜的 CD 和 UV-vis 吸收光谱与十二烷中的浓溶液相似，但 g 值更高。具体转...

  DOI：

  10.1021/ja983248l
• 作为产物：
  描述：

  4,5-bis(triisopropylsiloxy)-2,7-bis[1-(triisopropylsiloxy)ethenyl]naphthalene 在 cesium fluoride 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 180.0h， 生成 helicenebisquinone
  参考文献：
  名称：

  Expeditious Procedure To Synthesize Ethers and Esters of Tri- and Tetrahydroxy[6]helicenebisquinones from the Dye-Intermediates Disodium 4-Hydroxy- and 4,5-Dihydroxynaphthalene-2,7-disulfonates

  摘要：

  A procedure is described for synthesizing appreciable quantities of both the tetradodecyloxy[6]-helicenebisquinone 1 (R = dodecyl), which exhibits unique optical properties but previously was difficult to prepare, and a variety of analogues. The synthesis starts from disodium 4,5rlihvdroxynaphthalene-2, 7-disulfonate, the commercially available dye-interme diate known as chromotropic acid. It gives enantiopure 1, with R = (i-Pr)(3)Si, whose silyl groups can be replaced by dodecyl and hexanoyl groups. The same procedure applied to disodium 4-hydroxynaphthalene-2,7disulfonate, also an inexpensive, commercially available chemical, works equally well to produce the corresponding molecules that have one fewer side chain. Key steps are the use of tosyl groups to protect phenols and of a method described seven years ago by Satoh, Itoh, Miura, and Nomura to transform the sulfonic acid functions to iodides. The structure of tetra-(1S)-camphanate 20, the ester of the reduction product of (-)-1 [R = (i-Pr)(3)Si], was analyzed by X-ray diffraction. It shows the absolute configurations and supports the presumed basis for the rule that the (1S)-camphanates of(P)-helicen-1-ols are more polar than their (M)-diastereomers.

  DOI：

  10.1021/jo001356w

文献信息

• Synthesis, Structure, and Properties of a Helical Columnar Liquid Crystal
  作者：Colin Nuckolls、Thomas J. Katz

  DOI：10.1021/ja982025s

  日期：1998.9.1

  1 with the bis-hydroquinone that 1 gives when it is reduced. At room temperature, the nonracemic material forms a liquid crystalline phase, which upon heating becomes isotropic at 85 °C. Hexagonal columnar ordering in the pure material is demonstrated by X-ray diffraction, and columnar organization in dodecane solutions is indicated by all of the following increasing with concentration: the circular

  Helicene 2b 可以通过将 1 与 1 还原时产生的双氢醌结合形成的歧化产物酰化来制备。在室温下，非外消旋材料形成液晶相，加热后在 85 °C 时变为各向同性。X 射线衍射证明了纯材料中的六边形柱状排列，十二烷溶液中的柱状组织由以下所有随浓度增加而表示：圆二色性、比旋光度、荧光发射位移和 1H NMR 屏蔽。该材料是第一个具有非外消旋螺旋核的柱状中间相。
• Aggregation of Conjugated Helical Molecules
  作者：Colin Nuckolls、Thomas J. Katz、Louis Castellanos

  DOI：10.1021/ja960145z

  日期：1996.1.1
• Synthesis and Aggregation of a Conjugated Helical Molecule
  作者：Colin Nuckolls、Thomas J. Katz、Gail Katz、Peter J. Collings、Louis Castellanos

  DOI：10.1021/ja983248l

  日期：1999.1.1

  and the bis(triisopropylsilylenol ether) of a 2,7-diacetyl-4,5-dialkoxynaphthalene gives the helicene skeleton in 56% yield. Molecules of nonracemic 1 aggregate when their dodecane solutions are concentrated to 5 × 10-4 M or more. Chloroform dissociates the aggregates. Aggregation is characterized by enhanced circular dichroisms and g values, red-shifted UV−vis absorptions, increased specific rotations

  描述了合成螺旋双醌1的改进方法和通过分离衍生的莰酸酯来分离其对映体和其他螺旋双醌的对映体的有效方法。对苯醌与 2,7-二乙酰-4,5-二烷氧基萘的双（三异丙基甲硅烷醇醚）结合以 56% 的产率得到螺旋骨架。当十二烷溶液浓缩到 5 × 10-4 M 或更多时，非外消旋 1 的分子会聚集。氯仿分解聚集体。聚集的特征在于增强的圆二色性和 g 值、红移的 UV-vis 吸收、增加的比旋光度、增加吸收频率下的光散射，以及如前所述，转移到红色的荧光发射，1H NMR 共振转移高场，并将纯材料组织成纤维。旋涂薄膜的 CD 和 UV-vis 吸收光谱与十二烷中的浓溶液相似，但 g 值更高。具体转...
• Expeditious Procedure To Synthesize Ethers and Esters of Tri- and Tetrahydroxy[6]helicenebisquinones from the Dye-Intermediates Disodium 4-Hydroxy- and 4,5-Dihydroxynaphthalene-2,7-disulfonates
  作者：Kamil Paruch、Libor Vyklický、Thomas J. Katz、Christopher D. Incarvito、Arnold L. Rheingold

  DOI：10.1021/jo001356w

  日期：2000.12.1

  A procedure is described for synthesizing appreciable quantities of both the tetradodecyloxy[6]-helicenebisquinone 1 (R = dodecyl), which exhibits unique optical properties but previously was difficult to prepare, and a variety of analogues. The synthesis starts from disodium 4,5rlihvdroxynaphthalene-2, 7-disulfonate, the commercially available dye-interme diate known as chromotropic acid. It gives enantiopure 1, with R = (i-Pr)(3)Si, whose silyl groups can be replaced by dodecyl and hexanoyl groups. The same procedure applied to disodium 4-hydroxynaphthalene-2,7disulfonate, also an inexpensive, commercially available chemical, works equally well to produce the corresponding molecules that have one fewer side chain. Key steps are the use of tosyl groups to protect phenols and of a method described seven years ago by Satoh, Itoh, Miura, and Nomura to transform the sulfonic acid functions to iodides. The structure of tetra-(1S)-camphanate 20, the ester of the reduction product of (-)-1 [R = (i-Pr)(3)Si], was analyzed by X-ray diffraction. It shows the absolute configurations and supports the presumed basis for the rule that the (1S)-camphanates of(P)-helicen-1-ols are more polar than their (M)-diastereomers.