anti-<3.2>metacyclophanequinhydrone | 143309-53-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: anti-<3.2>metacyclophanequinhydrone
• 英文别名: 14,16-Dihydroxytricyclo[10.3.1.14,8]heptadeca-1(15),4,7,12(16),13-pentaene-6,17-dione
• CAS: 143309-53-9
• 化学式: C₁₇H₁₆O₄
• 分子量: 284.312
• InChiKey: ZXAIEHODVTXDGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  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 溶剂黄146 、 三氟乙酸 、 锌 、 thallium(III) trifluoroacetate 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 anti-<3.2>metacyclophanequinhydrone
  参考文献：
  名称：

  Medium-sized cyclophanes. Part 21. Preparation and reduction of syn- and anti-[3.2]metacyclophanequinone and anti-[4.2]metacyclophanequinone

  摘要：

  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.

  DOI：

  10.1021/jo00045a029

文献信息

• 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.