2-(2-bromoethylidene)adamantane | 90149-87-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 2-(2-bromoethylidene)adamantane
• 英文别名: 2-adamantilidylcarbinylbromide
• CAS: 90149-87-4
• 化学式: C₁₂H₁₇Br
• 分子量: 241.171
• InChiKey: SENNLDCHBRKAJP-VIJZIMQTSA-N

物化性质

• 沸点：
  298.8±9.0 °C(Predicted)
• 密度：
  1.419±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.76
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-(2-bromoethylidene)adamantane 在 氢氧化钾 、 硫酸 、 potassium iodide 作用下， 反应 16.25h， 生成 3',4'-dihydrospiro[adamantane-2,2'-benzo[h]chromene]-5',6'-dione
  参考文献：
  名称：

  .beta.-Lapachone: synthesis of derivatives and activities in tumor models

  摘要：

  In order to find a 3,4-dihydro-2H-naphtho[1,2-b]pyran-5,6-dione more potent than the naturally occurring 2,2-dimethyl derivative [beta-lapachone (10a)], we synthesized a series of analogous compounds with modifications at position 2 of the pyran ring or at positions 8 and 9 of the benzene ring. Of the compounds tested in vitro for inhibition of RNA-dependent DNA polymerase and in mice infected with Rauscher leukemia, all retained good enzyme activity. Inhibition of the reverse transcriptase activity of the 2,2-substituted derivatives 10b-e was as strong as 10a. However, only the 2-methyl-2-phenyl derivative 10e proved to be about as potent as the 2,2-dimethyl reference compound 10a in prolonging the mean survival time of mice with Rauscher leukemia virus induced leukemia.

  DOI：

  10.1021/jm00374a010
• 作为产物：
  描述：

  (adamantan-2-yliden)acetic acid ethyl ester 在 三溴化磷 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 3.0h， 生成 2-(2-bromoethylidene)adamantane
  参考文献：
  名称：

  Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via P^III/P^VRedox Cycling

  摘要：

  We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic, evidence supports the formation of a penta:coordinate (sigma(5)-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular docomposition of the sigma(5)-P hydridophosphorane via a conceited cyclic transition,structure that delivers the observed allylic transposition and completes a novel P-III/P-V redox Catalytic cycle. These results broaden the growing repertoire., of reactions catalyzed within the P-III/P-V redox couple and suggest additional opportunities for organophosphorus,catalysis in a biphilic mode.

  DOI：

  10.1021/jacs.5b01899

文献信息

• Synthesis of 1,2-Dihydroquinolines via Hydrazine-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis
  作者：Yunfei Zhang、Jae Hun Sim、Samantha N. MacMillan、Tristan H. Lambert

  DOI：10.1021/acs.orglett.0c02116

  日期：2020.8.7

  The synthesis of 1,2-dihydroquinolines by the hydrazine-catalyzed ring-closing carbonyl-olefin metathesis (RCCOM) of N-prenylated 2-aminobenzaldehydes is reported. Substrates with a variety of substitution patterns are shown. With an acid-labile protecting group on the nitrogen atom, in situ deprotection and autoxidation furnish quinoline. In comparison with related oxygen-containing substrates, the

  报道了通过N-异戊二烯基化 2-氨基苯甲醛的肼催化闭环羰基-烯烃复分解 (RCCOM) 合成 1,2-二氢喹啉。显示了具有多种替代模式的基材。氮原子上带有酸不稳定的保护基团，原位脱保护和自动氧化得到喹啉。与相关的含氧底物相比，催化循环的环加成步骤较慢，但发现环化更容易。
• Synthesis of 3,4-Disubstituted Piperidines by Carbonyl Ene and Prins Cyclizations:  Switching between Kinetic and Thermodynamic Control with Brønsted and Lewis Acid Catalysts
  作者：Jodi T. Williams、Perdip S. Bahia、Benson M. Kariuki、Neil Spencer、Douglas Philp、John S. Snaith

  DOI：10.1021/jo052532+

  日期：2006.3.1

  to cis and trans 3,4-disubstituted piperidines is described. Carbonyl ene cyclization of aldehydes 4a−e catalyzed by MeAlCl2 in refluxing chloroform afforded the trans piperidines 7a−e with diastereomeric ratios of up to 93:7, while aldehyde 4f afforded solely the cis product 6f, which was resistant to isomerization to the trans isomer. It was demonstrated for 4a that the cyclization catalyzed by a

  描述了一种新的顺式和反式3,4-二取代哌啶方法。在回流的氯仿中，MeAlCl 2催化的醛4a - e的羰基烯环化反应提供了高达93：7的非对映异构体比例的反式哌啶7a - e，而醛4f仅提供了顺式异构体6f，对顺反异构体具有抗性异构体。对于4a，证明了在动力学控制下进行的多种路易斯酸在低温下催化的环化反应主要得到顺式哌啶6a。，并在升温时异构化为热力学上更稳定的反式哌啶7a。与此相反，环化王子4A - ë浓盐酸在CH催化2氯2在低温下，得到顺式的哌啶6A - Ë最多的非对映体比率，以> 98:2。这些环化反应的收率和非对映选择性可以通过使用HCl饱和的CH 2 Cl 2形成相应的氯化物，然后除去氨影响的HCl来改善。醛4f和4g在后一种条件下也以良好的产率环化。DFT计算（B3LYP / 6-31G（d））支持的机理研究表明，环化反应是通过具有显着碳正离子特性的机理进行的，顺式碳正离子比反
• Photochromic spiropyran compounds
  申请人：GEC-MARCONI LIMITED

  公开号：EP0246114A2

  公开（公告）日：1987-11-19

  A series of novel photochromic spiropyrans are disclosed in which a spiro-adamantane group is introduced into the 2-position of the benzopyran or naphthopyran ring. The spiropyran compounds of the invention exhibit heliochromic properties, i.e. they colour in sunlight and fade rapidly at ambient temperatures in the absence of U.V. light, making them good candidates for use in the manufacture of sunglasses. The invention includes lenses which darken in sunlight and incorporate the novel spiro­pyrans and a process for the preparation of the spiropyran compounds.

  本发明公开了一系列新型光致变色螺吡喃，其中苯并吡喃或萘并吡喃环的 2 位引入了一个螺金刚烷基团。本发明的螺吡喃化合物具有日光变色特性，即在阳光下着色，在没有紫外光的环境温度下迅速褪色，因此是制造太阳镜的理想材料。本发明包括在阳光下变黑并含有新型螺吡喃的镜片和制备螺吡喃化合物的工艺。
• Synthesis and aqueous reactivity of n-adamantylidylcarbinyl-n,n-dimethyl-4-cyanoanilinium bromide
  作者：Barry L Knier、Carmen L Rodríguez

  DOI：10.1016/s0040-4039(00)98957-3

  日期：1985.1
• KNIER, B. L.;RODRIGUEZ, C. L., TETRAHEDRON LETT., 1985, 26, N 18, 2183-2186
  作者：KNIER, B. L.、RODRIGUEZ, C. L.

  DOI：——

  日期：——