syn-9,18-difluoro-2,11-dithia<3.3>metacyclophane | 106972-81-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: syn-9,18-difluoro-2,11-dithia<3.3>metacyclophane
• 英文别名: 9,18-difluorodithia<3.3>metacyclophane；syn-9,18-difluoro-2,11-dithia[3.3]metacyclophane；17,18-difluoro-3,11-dithiatricyclo[11.3.1.15,9]octadeca-1(17),5(18),6,8,13,15-hexaene
• CAS: 106972-81-0；25117-62-8
• 化学式: C₁₆H₁₄F₂S₂
• 分子量: 308.416
• InChiKey: UEUMWJGIQKVNRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.15
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  syn-9,18-difluoro-2,11-dithia<3.3>metacyclophane 生成 syn/anti-8,16-difluoro<2.2>metacyclophane
  参考文献：
  名称：

  以氢和氟的相对大小为取代基。-到[2.2]甲基环戊烯异构化的两种途径：带有内部氟取代基的第一个二氢py的合成

  摘要：

  先前要求保护的-8，1.6-二氟[2.2]间环烷和间环-1，9-二烯显示为-异构体。正品-异构体通过用铬三羰基，这使得纯前体环芳的芳烃环的络合得到异构体被分离并转化为产品。所述的异构化-二氟异构体的异构体出现在高得多的温度（300℃），比将在类似的甲基的基础上可以预料（196℃）或氢（0℃）的化合物。对bridge-SMe取代实例的分析清楚地表明，在的异构化过程中必须发生桥裂，而在，因此取决于内部取代基，两种不同的途径是有效的。该二烯在升温价异构化成桥接[14]轮烯，所述difluorodlhydropyrene ，具有比烷基或芳基等的取代基内的第一个例子。

  DOI：

  10.1016/0040-4039(88)85142-6
• 作为产物：
  描述：

  2,6-双(溴甲基)氟苯 在 氢氧化钾 作用下， 以 乙醇 、 苯 为溶剂， 反应 10.0h， 生成 syn-9,18-difluoro-2,11-dithia<3.3>metacyclophane
  参考文献：
  名称：

  Preparation and NMR properties of tricarbonylchromium(0) derivatives of dithiacyclophanes. An estimate of the reduction in ring current of an aromatic ring on tricarbonylchromium complexation

  摘要：

  DOI：

  10.1021/jo00286a016

文献信息

• Metacyclophanes and related compounds. 22. Medium-sized cyclophanes. Preparation and valence tautomerism of 8,16-disubstituted [2.2]metacyclophane-1,9-dienes
  作者：Takehiko Yamato、Akira Miyazawa、Masashi Tashiro

  DOI：10.1021/jo00027a047

  日期：1992.1

  Introduction of functional groups other than hydrogen or alkyl groups into the internal positions of [2.2]metacyclophane-1,9-dienes was attempted. [2.2]Metacyclophane-1,9-dienes 6a-6g, bearing variously halogen, methoxy, and methyl substituents in the 8 and 16 positions, were prepared from the corresponding bis(halomethyl)benzenes 1 and bis(mercaptomethyl)benzenes 2 involving use of Wittig rearrangement of 2,11-dithia-[3.3]metacyclophanes followed by Hofmann elimination. Although 6a-6c, 6f, and 6g were isolated as thermally stable crystals, isolation of 6d failed since this compound was thermally labile and transformed spontaneously into 2,7-di-tert-butyl-1-chloropyrene (7). The photochemical and thermal valence tautomerizations of [2.2]metacyclophanes which were prepared in the present work are described. Attempts to convert 8,16-disubstituted [2.2]metacyclophane-1,9-dienes 6 to 4,5,9,10-tetrabromo-10b,10c-disubstituted 10b,10c-dihydropyrenes by treatment of these compounds with bromine in carbon tetrachloride failed but instead gave addition products 13 and transannular reaction products 14. The reaction pathways of the bromination are also discussed.
• Voegtle,F., Angewandte Chemie, 1969, vol. 81, p. 258 - 259
  作者：Voegtle,F.

  DOI：——

  日期：——
• MITCHELL, REGINALD H.;BODWELL, GRAHAM J.;VINOD, THOTTUMKARA K.;WEERAWARNA+, TETRAHEDRON LETT., 29,(1988) N 27, C. 3287-3290
  作者：MITCHELL, REGINALD H.、BODWELL, GRAHAM J.、VINOD, THOTTUMKARA K.、WEERAWARNA+

  DOI：——

  日期：——
• Preparation and NMR properties of tricarbonylchromium(0) derivatives of dithiacyclophanes. An estimate of the reduction in ring current of an aromatic ring on tricarbonylchromium complexation
  作者：Reginald H. Mitchell、Thottumkara K. Vinod、Graham J. Bodwell、Gordon W. Bushnell

  DOI：10.1021/jo00286a016

  日期：1989.12
• On the relative sizes of hydrogen and fluorine as substituents. Two pathways for the isomerization of - to -[2.2]metacyclophanes
  作者：Reginald H. Mitchell、Graham J. Bodwell、Thottumkara K. Vinod、Kumudini S. Weerawarna

  DOI：10.1016/0040-4039(88)85142-6

  日期：1988.1

  The previously claimed -8,1.6-difluoro[2.2]metacyclophane and metacyclophane-1,9-diene were shown to be -isomers. The authentic -isomers were obtained by complexation of the arene rings of the precursor cyclophanes with a chromium tricarbonyl group, which enables pure -isomers to be separated and transformed to products. The isomerization of the -difluoro isomer to the -isomer occurs at much higher

  先前要求保护的-8，1.6-二氟[2.2]间环烷和间环-1，9-二烯显示为-异构体。正品-异构体通过用铬三羰基，这使得纯前体环芳的芳烃环的络合得到异构体被分离并转化为产品。所述的异构化-二氟异构体的异构体出现在高得多的温度（300℃），比将在类似的甲基的基础上可以预料（196℃）或氢（0℃）的化合物。对bridge-SMe取代实例的分析清楚地表明，在的异构化过程中必须发生桥裂，而在，因此取决于内部取代基，两种不同的途径是有效的。该二烯在升温价异构化成桥接[14]轮烯，所述difluorodlhydropyrene ，具有比烷基或芳基等的取代基内的第一个例子。