4-(epoxymethylene)protoadamantane | 59182-37-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: 4-(epoxymethylene)protoadamantane
• 英文别名: 4-epoxymethyleneprotoadamantane；epoxymetyleneprotoadamantane；4-Epoxymethylenprotoadamantan；Spiro[oxirane-2,4'-tricyclo[4.3.1.03,8]decane]
• CAS: 59182-37-5；59204-01-2；65556-89-0
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: TUDXPALPONWYFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(epoxymethylene)protoadamantane 在 硫酸 作用下， 以 丙酮 为溶剂， 生成 2-hydroxy-1-adamantanomethanol
  参考文献：
  名称：

  Solvolysis of 1-substituted-2-adamantyl sulfonates. Bridging or no bridging?

  摘要：

  DOI：

  10.1021/ja00433a041
• 作为产物：
  描述：

  4-protoadamantanone 、 三甲基碘化亚砜 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 11.0h， 生成 4-(epoxymethylene)protoadamantane
  参考文献：
  名称：

  Anti-allodynic effect of 2-(aminomethyl)adamantane-1-carboxylic acid in a rat model of neuropathic pain: A mechanism dependent on CaV2.2 channel inhibition

  摘要：

  Neuropathic pain is a serious physical disabling condition resulting from lesion or dysfunction of the peripheral sensory nervous system. Despite the fact that the mechanisms underlying neuropathic pain are poorly understood, the involvement of voltage-gated calcium (Ca-V) channels in its pathophysiology has justified the use of drugs that bind the Ca-V channel alpha(2)delta auxiliary subunit, such as gabapentin (GBP), to attain analgesic and anti-allodynic effects in models involving neuronal sensitization and nerve injury. GBP binding to alpha(2)delta inhibits nerve injury-induced trafficking of the alpha(1) pore forming subunits of Ca-V channels, particularly of the N-type, from the cytoplasm to the plasma membrane of pre-synaptic terminals in dorsal root ganglion neurons and dorsal horn spinal neurons. In the search for alternative forms of treatment, in this study we describe the synthesis and pharmacological profile of a GABA derivative, 2-aminoadamantane-1-carboxylic acid (GZ4), which displays a close structure-activity relationship with GBP. Behavioral assessment using von Frey filament stimuli showed that GZ4 treatment reverted mechanical allodynia/hyperalgesia in an animal model of spinal nerve ligation-induced neuropathic pain. In addition, using the patch clamp technique we show that GZ4 treatment significantly decreased whole-cell currents through N-type Ca-V channels heterologously expressed in HEK-293 cells. Interestingly, the behavioral and electrophysiological time course of GZ4 actions reflects that its mechanism of action is similar but not identical to that of GBP. While GBP actions require at least 24 h and imply uptake of the drug, which suggests that the drug acts mainly intracellularly affecting channels trafficking to the plasma membrane, the faster time course (1-3 h) of GZ4 effects suggests also a direct inhibition of Ca2+ currents acting on cell surface channels. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2014.02.006

文献信息

• Syntheses of 1,2-distributed adamantanes
  作者：Ashraf N. Abdel-Sayed、Ludwig Bauer

  DOI：10.1016/s0040-4020(01)90330-8

  日期：1988.1

  addition and rearrangement of 2 with hydrohalic acids there were obtained excellent yields of 2-halo-l-adamantanols and 1,2-dihaloadamantanes. 2-Halo-l-adamantanols served as starting materials for the synthesis of twelve additional 1,2- dihaloadamantanes. The boron trifluoride catalyzed reaction of 2 with acetic anhydride furnished 1,2-diacetoxyadamantane in 84% yield. Mechanisms for these various reactions

  4-外-和4-内-环氧亚甲基原金刚烷（1）和4-原金刚烷酮（2）的亲电催化反应提供了各种1,2-二取代的金刚烷。1与路易斯酸（例如氯化铝，溴化物和碘化物）在-78°C下的反应以优异的收率得到了2-氯-，2-溴-和2-碘-1-（羟甲基）金刚烷。当1与三氟化硼反应形成2-氟-1-（羟甲基）金刚烷时，发生了有趣的氟离子转移。1在溴化铝存在下与苯反应生成1-（羟甲基）-2-苯基金刚烷，产率为70％。通过酸催化的2的加氢卤代酸的加成和重排，获得了优异的2-卤代-1-金刚烷醇和1，2-二重金刚烷烷的产率。2-卤代-1-金刚烷醇用作合成另外十二种1,2-二卤代金刚烷烷的起始原料。三氟化硼催化的2与乙酸酐的反应以84％的收率提供了1,2-二乙酰氧基金刚烷。讨论了这些各种反应的机理。
• Dihaloadamantanes: Ring Closure versus Rearrangement or Halogen-Displacement Reactions
  作者：Kata Mlinarić-Majerski、Jelena Veljković、Mira Kaselj、Alan P. Marchand

  DOI：10.1002/ejoc.200400121

  日期：2004.7

  corresponding ring-closing reactions, performed by using Na metal or alkyllithium reagents, were studied. Compound 1 reacted with Na in toluene or in tetraglyme to afford 1,2-methanoadamantane (4) as the major product. However, the corresponding reactions, when performed by using 2 and 3 as substrates, produced methyladamantane (5) or 4-methyleneprotoadamantane (6) as the major reaction products. The corresponding

  合成了三种二卤代金刚烷 [即 2-溴-1-(氯甲基)金刚烷 (1)、1-(溴甲基)-2-氯金刚烷 (2) 和 2-溴-1-(溴甲基)金刚烷 (3)]，并且研究了它们通过使用金属钠或烷基锂试剂进行的相应闭环反应。化合物 1 在甲苯或四甘醇二甲醚中与 Na 反应，得到 1,2-甲基金刚烷 (4) 作为主要产物。然而，相应的反应，当使用 2 和 3 作为底物时，产生甲基金刚烷 (5) 或 4-亚甲基原金刚烷 (6) 作为主要反应产物。1 和 2 与 tBuLi 或 nBuLi 的相应反应得到少量 4、5 和 6 以及相应的单卤化物，即 1-(氯甲基)金刚烷 (7) 和 2-氯-1-甲基金刚烷 (8)，它们构成了这些反应的主要产物。
• Chakrabarti,J.K. et al., Journal of the Chemical Society. Perkin transactions I, 1976, p. 1893 - 1900
  作者：Chakrabarti,J.K. et al.

  DOI：——

  日期：——
• 1,2-Methanoadamantane: A Molecule with a Twist Bent .sigma. Bond
  作者：Kata Mlinaric-Majerski、Mira Kaselj

  DOI：10.1021/jo00095a004

  日期：1994.8

  The reaction of 1-(chloromethyl)-2-bromoadamantane with sodium leads to ring closure to the hitherto unknown 1,2-methanoadamantane (1). Reactivity studies of 1 provide strong evidence for the existence of a twist bent a bond.
• ABDEL-SAYED, ASHRAF N.;BAUER, LUDWIG, TETRAHEDRON, 44,(1988) N 7, 1873-1882
  作者：ABDEL-SAYED, ASHRAF N.、BAUER, LUDWIG

  DOI：——

  日期：——