5,12-methano<2.2.2>paracyclophan-25-one | 57468-28-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 二苯并环庚烯
• 英文名称: 5,12-methano<2.2.2>paracyclophan-25-one
• 英文别名: 5,12-methano[2.2.2]paracyclophan-25-one；Pentacyclo[14.3.2.27,10.14,19.113,17]pentacosa-1(19),2,4(22),7,9,13(23),14,16,24-nonaen-18-one
• CAS: 57468-28-7
• 化学式: C₂₅H₂₂O
• 分子量: 338.449
• InChiKey: XVLFEOUQYMGPTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5,12-methano<2.2.2>paracyclophan-25-one 在 sodium hydroxide 、 肼 作用下， 以 二乙二醇 为溶剂， 生成 5,12-methano<2.2.2>paracyclophane
  参考文献：
  名称：

  三[2.2.2]对二甲苯假双生酮一些衍生物的制备及性质

  摘要：

  制备了三[2.2.2]对二甲苯(I)的假孪生酮的一些衍生物，并结合它们的结构特征研究了它们的光谱性质。三 [2.2.2] 对二甲苯（III 和 V）的假双生甲醇的两种异构体的立体化学是根据 NMR 光谱中二苯甲基质子和 Ho 质子的化学位移以及红外光谱中的 νO-H 谱带确定的. 两种醇的 Hp 质子化学位移的差异可以用对位碳原子的电子密度变化来解释。

  DOI：

  10.1246/bcsj.49.529
• 作为产物：
  描述：

  4-Carboxy<2.2.2>paracyclophane 在 zinc(II) chloride 、 三氯氧磷 作用下， 生成 5,12-methano<2.2.2>paracyclophan-25-one
  参考文献：
  名称：

  三[[2.2.2]-]和四[2.2.2.2]对亚苄基的假双酮的制备及性质

  摘要：

  制备了三[2.2.2]对亚二甲苯基1和四[2.2.2.2]对亚二甲苯基2的假基因桥联酮，并与二苯并亚砜3进行了比较，研究了其光谱性质。的CO伸缩的带1在异常高的频率区域中观察到（通过约50厘米-1）与比较3，而的2是在类似于的位置3。电子光谱1表明，由于CO和芳烃之间缺乏共面性，因此1具有极大的共轭损失。H 0的化学位移，邻位到CO，的1也支持这一结构特征。

  DOI：

  10.1016/0040-4020(75)87036-0

文献信息

• Exploring the Chemistry of [2.2.2]Paracyclophane
  作者：Henning Hopf、Verena Lehne、Ludger Ernst

  DOI：10.1055/s-0035-1561483

  日期：——

  Starting with the parent compound [2.2.2]paracyclophane several routes were developed to synthesize its 4-vinyl derivative. From the 4-aldehyde and the bromomethyl derivative the stilbenophanes were prepared which photocyclize to the phenanthrenophanes. A new route to a bridged ketone was developed which was subjected to the addition of phenyllithium and to typical aromatic substitution reactions (inter

  从母体化合物 [2.2.2] 对环芳开始，开发了几种合成其 4-乙烯基衍生物的路线。由4-醛和溴甲基衍生物制备芪酚，其光环化为菲酚。开发了一种新的桥接酮路线，该路线经历了苯基锂的加成和典型的芳香族取代反应（尤其是里什甲酰化、弗里德尔-克拉夫茨酰化）。桥接酮的溴化产生了一种不寻常的托酮衍生物。还对桥连烃（桥连酮的还原产物）进行了亲电取代反应。对于桥连酮和桥连烃，亲电取代发生区域选择性，有利于分别以顺式方向​​将新取代基引入桥接酮基和亚甲基基团。1 引言 2 结果与讨论 2.1 4-乙烯基[2.2.2] 对环烷 (5) 2.2 [2.2.2] 对环烷 (2a) 作为扩展芳烃系统的一部分 2.3 5,12-甲醇 [2.2.2] 对环烷的制备-25-one ( 3 ) 2.4 与 5,12-Methano[2.2.2] paracyclophan-25-one ( 3 ) 的选择性反应 2.4.1
• Metallocenophanes. Part VI. 5,12-Methano[2.2.2]paracyclophane: a new ligand for .pi.-complexation in a cavity. Improved synthesis and the characterization of its silver(I) perchlorate complex
  作者：Fenton R. Heirtzler、Henning Hopf、Peter G. Jones、Peter Bubenitschek、Verena Lehne

  DOI：10.1021/jo00062a021

  日期：1993.5

  The consequences of a bridging methylene group in 1, i.e. as in 2, on the geometry and ability to complex Ag(I) were studied. Compound 2 was prepared in three steps and 36% overall yield from 1 in a new procedure and characterized through X-ray crystallography. The X-ray crystal structure of its endo complex (3) with AgClO4 shows three independent molecules in the crystal lattice. The geometry of the ligand in 3 is like that in 2. Ag is 2.48-3.00 angstrom from the nearest Ar-C, is 0.13-0.31 angstrom outside of the cavity of 2, and binds nearly symmetrically across the C(5)-C)6), C(11)-C(12), and C(23)-C(24) bonds. Compound 2 is shown to be a weaker complexing agent for Ag(I) than [2.2.2]-paracyclophane. Practical and theoretical ramifications of the bonding mode are discussed.
• TABUSHI I.; YOSHIDA Z.; IMISHIRO F., TETRAHEDRON <TETR-AB>, 1975, 31, NO 16, 1833-1836
  作者：TABUSHI I.、 YOSHIDA Z.、 IMISHIRO F.

  DOI：——

  日期：——
• Preparations and Properties of Some Derivatives of Pseudo-Geminal Ketone of Tris[2.2.2]paraxylylene
  作者：Fumio Imashiro、Zen-ichi Yoshida、Iwao Tabushi

  DOI：10.1246/bcsj.49.529

  日期：1976.2

  Some derivatives of pseudo-geminal ketone of tris[2.2.2]paraxylylene (I) were prepared and their spectral properties were investigated in connection with their structural characteristics. The stereochemistry of two isomers of pseudo-geminal carbinols of tris[2.2.2]paraxylylene (III and V) was determined on the basis of chemical shifts of benzhydryl protons and Ho protons in NMR spectra and also of

  制备了三[2.2.2]对二甲苯(I)的假孪生酮的一些衍生物，并结合它们的结构特征研究了它们的光谱性质。三 [2.2.2] 对二甲苯（III 和 V）的假双生甲醇的两种异构体的立体化学是根据 NMR 光谱中二苯甲基质子和 Ho 质子的化学位移以及红外光谱中的 νO-H 谱带确定的. 两种醇的 Hp 质子化学位移的差异可以用对位碳原子的电子密度变化来解释。
• Preparations and properties of pseudo-geminal ketones of tris-[2.2.2]- and tetrakis[2.2.2.2]parazylylene
  作者：I. Tabushi、Z. Yoshida、F. Imishiro

  DOI：10.1016/0040-4020(75)87036-0

  日期：1975.1

  Pseudo-geminal bridged ketones of tris[2.2.2]paraxylylene, 1, and of tetrakis[2.2.2.2]paraxylylene, 2, were prepared and their spectral properties were investigated in comparison with those of dibenzosuberone, 3. The CO stretching band of 1 was observed at abnormally high frequency region (by ca. 50 cm−1) compared with that of 3, while that of 2 was at a position similar to that of 3. The electronic

  制备了三[2.2.2]对亚二甲苯基1和四[2.2.2.2]对亚二甲苯基2的假基因桥联酮，并与二苯并亚砜3进行了比较，研究了其光谱性质。的CO伸缩的带1在异常高的频率区域中观察到（通过约50厘米-1）与比较3，而的2是在类似于的位置3。电子光谱1表明，由于CO和芳烃之间缺乏共面性，因此1具有极大的共轭损失。H 0的化学位移，邻位到CO，的1也支持这一结构特征。