6,14-Di-tert-butyl-tricyclo[10.3.1.1^4,8]heptadeca-1(16),4(17),5,7,12,14-hexaene-16,17-diol | 142838-69-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 6,14-Di-tert-butyl-tricyclo[10.3.1.1^4,8]heptadeca-1(16),4(17),5,7,12,14-hexaene-16,17-diol
• 英文别名: 6,14-ditert-butyltricyclo[10.3.1.14,8]heptadeca-1(15),4,6,8(17),12(16),13-hexaene-16,17-diol
• CAS: 142838-69-5
• 化学式: C₂₅H₃₄O₂
• 分子量: 366.544
• InChiKey: HLHSHBBPFOMPJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.97
• 重原子数：
  27.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  6,14-Di-tert-butyl-tricyclo[10.3.1.1^4,8]heptadeca-1(16),4(17),5,7,12,14-hexaene-16,17-diol 在 三氯化铝 、 苯 作用下， 以 硝基甲烷 为溶剂， 反应 24.0h， 以76%的产率得到9,17-Epoxy<3.2>metacyclophane
  参考文献：
  名称：

  Yamato, Takehiko; Matsumoto, Jun-ichi; Tokuhisa, Kiwamu, Chemische Berichte, 1992, vol. 125, # 11, p. 2443 - 2454

  摘要：

  DOI：
• 作为产物：
  描述：

  anti-6,14-Di-tert-butyl-9,17-dimethoxy<3.2>metacyclophane 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以83%的产率得到6,14-Di-tert-butyl-tricyclo[10.3.1.1^4,8]heptadeca-1(16),4(17),5,7,12,14-hexaene-16,17-diol
  参考文献：
  名称：

  Yamato, Takehiko; Matsumoto, Jun-ichi; Tokuhisa, Kiwamu, Chemische Berichte, 1992, vol. 125, # 11, p. 2443 - 2454

  摘要：

  DOI：

文献信息

• The preparation and novel [3.3] sigmatropic rearrangement of cyclophanes having a spiro skeleton
  作者：Takehiko Yamato、Jun-ichi Matsumoto、Kiwamu Tokuhisa、Kazuaki Suehiro、Masashi Tashiro

  DOI：10.1039/c39920000865

  日期：——

  intramolecular O–C coupling product 2, which has a spiro skeleton in good yield; variable temperature 1H NMR measurements indicated that compounds 2 are interconvertible by a thermal [3.3] sigmatropic rearrangement, and the activation free energies for the [3.3] sigmatropic rearrangement increased with increasing length of the methylene bridge in compounds 2.

  用K 3 [Fe（CN）6 ]氧化二羟基[ n .2]甲基环已烷1可以得到分子内的O-C偶联产物2，该产物具有螺旋骨架，收率很高。可变温度1 H NMR测量表明，化合物2通过热[3.3]σ重排可相互转换，并且[3.3]σ重排的活化自由能随化合物2中亚甲基桥长度的增加而增加。
• Yamato, Takehiko; Matsumoto, Jun-ichi; Sato, Mitsuhiro, Journal of Chemical Research, Miniprint, 1997, # 3, p. 518 - 529
  作者：Yamato, Takehiko、Matsumoto, Jun-ichi、Sato, Mitsuhiro、Fujita, Koji、Nagano, Yoshiaki

  DOI：——

  日期：——
• Yamato, Takehiko; Matsumoto, Jun-Ichi; Fujita, Koji, Journal of the Chemical Society. Perkin transactions I, 1998, # 1, p. 123 - 129
  作者：Yamato, Takehiko、Matsumoto, Jun-Ichi、Fujita, Koji

  DOI：——

  日期：——
• Medium-sized cyclophanes. Part 21. Preparation and reduction of syn- and anti-[3.2]metacyclophanequinone and anti-[4.2]metacyclophanequinone
  作者：Takehiko Yamato、Junichi Matsumoto、Masami Kajihara、Kiwamu Tokuhisa、Kazuaki Suehiro、Masashi Tashiro

  DOI：10.1021/jo00045a029

  日期：1992.9

  The title compounds, anti- and syn-[3.2]metacyclophanequinone (12a) and (12b), were prepared by oxidation of the corresponding anti- and syn-9,17-dihydroxy-6,14-di-tert-butyl[3.2]metacyclophanes (10a) and (10b) with Tl(OCOCF3)3 in CF3COOH. When anti-13.2]quinonophane (12a) was reduced with Zn powder in acetic acid, the corresponding tetrahydroxy derivative 14a was obtained, which was converted to the quinhydrone 13a by treatment with an equimolar amount of quinonophane 12a in refluxing THF. The electronic spectrum of 13a shows a band due to a charge-transfer complex at 400 nm (log-epsilon 2.45). In contrast, attempted reduction of syn-quinonophane (12b) with Zn powder in acetic acid yielded only a complex mixture of products. It was also found that syn-quinonophane was easily converted to the corresponding [2 + 2] cycloadducts 16 and 17 by irradiation with sunlight or tungsten lamp. When oxidation of anti- and syn-10,18-dihydroxy-7,15-di-tert-butyl[4.2]-metacyclophanes (11a) and (11b) with Tl(OCOCF3)3 in CF3COOH was carried out under the same conditions as [3.2]metacyclophanes, both compounds gave anti-metacyclophanequinone (18a). This finding suggests that the ring inversion to the thermodynamically more stable anti conformation is possible in the [4.2]metacyclophanequinone. While anti-[4.2]metacyclophanequinone (18a) was reduced with Zn powder in acetic acid, the color change of reaction mixture from pale yellow to reddish brown was observed due to the formation of the corresponding quinhydrone 19. However, the attempted isolation of the quinhydrone 19 was unsuccessful. Rather, the fully reduced tetrahydroxy derivative 20 was obtained in 91 % yield.