2-syn,3-syn,5-syn,6-syn-tetrakis(hydroxymethyl)bicyclo[2.2.2]oct-7-ene | 62234-71-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-syn,3-syn,5-syn,6-syn-tetrakis(hydroxymethyl)bicyclo[2.2.2]oct-7-ene
• 英文别名: 2-syn,3-syn,5-syn,6-syn-tetrakis(hydroxymethyl)bicyclo<2.2.2>oct-7-ene；2-syn, 3-syn, 5-syn, 6-syn-tetrahydroxymethylbicyclo<2.2.2>oct-7-ene；all-exo-5,6,7,8-Tetrakis(hydroxymethyl)bicyclo<2.2.2>oct-2-en；exo-2,3,5,6-tetrakis(hydroxymethyl)bicyclo<2.2.2>oct-7-ene；bicyclo<2.2.2>oct-7-ene-2syn,3syn,5syn,6syn-tetramethanol；all-exo-5,6,7,8-Tetrakis(hydroxymethyl)bicyclo[2.2.2]oct-2-en
• CAS: 62234-71-3
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: MOAKAWNYCNNZJR-KUDAMMAASA-N

物化性质

• 熔点：
  180-181 °C(Solv: ethanol (64-17-5))
• 沸点：
  396.5±27.0 °C(Predicted)
• 密度：
  1.198±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.76
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  80.92
• 氢给体数：
  4.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-syn,3-syn,5-syn,6-syn-tetrakis(hydroxymethyl)bicyclo[2.2.2]oct-7-ene 以70%的产率得到
  参考文献：
  名称：

  GABIOUD, R.;VOGEL, P., HELV. CHIM. ACTA, 1983, 66, N 4, 1134-1147

  摘要：

  DOI：
• 作为产物：
  描述：

  tetraethyl bicyclo[2.2.2]oct-7-ene-2-syn,3-syn,5-syn,6-syn-tetracarboxylate 在 lithium aluminium tetrahydride 作用下， 生成 2-syn,3-syn,5-syn,6-syn-tetrakis(hydroxymethyl)bicyclo[2.2.2]oct-7-ene
  参考文献：
  名称：

  5,6,7,8-四亚甲基-2-双环[2.2.2]辛醇和-辛酮的合成和狄尔斯-阿尔德反应性。相应的双（三羰基铁）配合物的选择性氧化†

  摘要：

  所述的硼氢化顺，反- [铁（CO）3 ] 2双复数24容易获得的5,6,7,8- tetramethylidene -2-双环[2.2.2]辛烯（22），得到相应的双络合2 -双环[2.2.2]辛醇25. CrO 3-氧化制得的酮27。用三甲基氧化胺选择性地氧化25和27中的顺式-Fe（CO）3-基团，得到相应的抗-Fe（CO 3）-单络合四烯26和28。可以除去28中的抗-Fe（CO）3-基团，得到5,6,7,8-四亚甲基-2-双环[2.2.2]辛酮（11）。加入NaBH 4的-还原11得到tetraenol 10. TCE-环加成到10和11（ķ 1）分别为至少10倍的速度的那些（ķ 2）为相应的单加成物35/36和34，分别。此狄尔斯-阿尔德反应速度差消失（ķ 1 ≈ ķ 2）与丙酸甲酯。后者的亲二烯体以“对”-区域选择性加到抗-Fe（CO）3-单络合物的四烯酮28中。

  DOI：

  10.1002/hlca.19830660417

文献信息

• Bicyclo[2.2.2]octane-capped porphyrins. 1. Synthesis, characterization, and solution three-dimensional structure
  作者：Hong Yue Zhang、Andrei Blasko、Jian Qiu Yu、Thomas C. Bruice

  DOI：10.1021/ja00043a003

  日期：1992.8

  novel capped porphyrins bicyclo [2.2.2]octane-capped porphyrins, VIAH 2 and VIBH 2 , and bicyclo [2.2.2]- oct-7-ene-capped porphyrin, VICH 2 } have been successfully synthesized by the Lewis acid (BF 3 .Et 2 O) catalyzed condensation of pyrrole with tetraacetals 6, 12, and 15, respectively. 1 H and 13 C 1D and 1 H- 1 H 2D NMR (DQF-COSY and ROESY) of porphyrins VIAH 2 and VIBH 2 and 1 H 1D and 2D NMR

  路易斯酸成功合成了三种新型封端卟啉双环[2.2.2]辛烷封端卟啉VIAH 2 和VIBH 2 和双环[2.2.2]-oct-7-烯封端卟啉VICH 2 } (BF 3 .Et 2 O) 分别催化吡咯与四缩醛 6、12 和 15 的缩合。卟啉 VIAH 2 和 VIBH 2 的 1 H 和 13 C 1D 和 1 H- 1 H 2D NMR（DQF-COSY 和 ROESY）以及 VICH 2 的 1 H 1D 和 2D NMR 确定了双环 [2.2.2] 的桥辛烷帽指向帽和卟啉平面之间形成的空腔外部。VIAH 2 在溶液中的三维结构已经使用 ROESY 和距离几何计算确定，并且卟啉和帽之间形成的空腔已被证明是仅足以容纳单个 H 2 O。
• Synthesis of a spheroidal bis-porphyrin: a ligand designed to accept two catalytic metal ions in an isolated environment
  作者：Zhang Hong-Yue、Yu Jian-Qiu、Thomas C. Bruice

  DOI：10.1016/s0040-4020(01)89277-2

  日期：1994.1

  and catalase, has been synthesized in 9 steps. C-Alkylation of 2-(2′-lithio-5′-tert-butyldimethylsiloxy-methyl)phenyl-1,3-dioxolane (D) with tetra-bromide 6, prepared from bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride by 5 steps, afforded the key intermediate, tetra-alkylated compound 3a, in 68% yield. An alternative route to 3, O-alkylations of tetrol 4 with aliphatic halides 5, was also

  已经设计了一个球形双卟啉（双封端的四联共界面二聚四苯基卟啉，1），设计用作模拟超氧化物歧化酶和过氧化氢酶组合酶活性的一类催化剂的配体。2-（2'-锂代-5'-的C-烷基化叔-butyldimethylsiloxy甲基）苯基-1,3-二氧戊环（d）与四溴化6，从二环〔2,2,2〕辛-7-烯通过5个步骤，将-2,3,5,6-四羧酸二酐得到68％的收率的关键中间体四烷基化化合物3a。到替代路线3四醇的，O-烷基化4用的脂族卤化物5，也经过测试。四个受保护的羟基向溴取代基的转化对于卟啉2的制备至关重要。因此，制备四苄基溴化物24b，然后在三氟化硼醚化物的存在下用吡咯处理，然后进行DDQ氧化，得到封端的卟啉2。两个分子的联接2以形成球状卟啉1在稀DMF溶液中进行，使用0.8当量的2- trimethylsilylethane磺酰胺（H 2 NSO 2 CH 2 CH 2的Si（CH 3）3，SES-NH
• Atzkern, Hermann; Koehler, Frank H.; Mueller, Reinhard, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1990, vol. 45, # 3, p. 329 - 343
  作者：Atzkern, Hermann、Koehler, Frank H.、Mueller, Reinhard

  DOI：——

  日期：——
• <i>exo,exo</i>-4,8-Ethenopolyfluoro-2,6-dioxaperhydroindacenes. Unusual Alkenes Flanked with Fluorine Atoms
  作者：Wojciech Dmowski、Ireneusz Nowak、Przemysław Gluziński、Andrei Kemme

  DOI：10.1021/jo962023v

  日期：1997.3.1

  Unusual alkenes, exo,exo-4,8-etheno-1,1,3,3,5,5,7,7-octafluoro-2,6-dioxaperhydro-s-indacene (1) and exo,exo-4,8-etheno-1,1,3,3-tetrafluoro-2,6-dioxaperhydroindacene (2), as well as their nonfluorinated analogue 3 were synthesized. The structures of 1 and 3 have been determined in the solid state by X-ray crystallography and of all three compounds in solution by H-1, F-19, and C-13 NMR spectroscopy. The chemical. properties of compounds 1-3 were investigated and compared, The double bond in fluorinated polycycloalkenes 1 and 2 was found to be totally inert toward bromination, hydrogenenation, and oxidation with m-chloroperbenzoic acid and ozone. This is in contrast to nonfluorinated indacene 3, which behaves like a normal alkene, readily adds bromine and hydrogen, and reacts with oxidants. The only successful chemical transformation of I was achieved by treatment with Mn2O7, which led to oxirane 15 and rearranged pentacyclic acetal 16. An interesting skeletal rearrangement occurred in the course of bromination of 3 leading to bicyclic tetrabromo derivative 12. High chemical inertness of polyfluoroindacenes 1 and 2 has been attributed mainly to through-space electronic interactions of the double bond with proximal fluorine atoms.