2-exo-phenyloxybicyclo[2.2.1]heptane | 50414-49-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-exo-phenyloxybicyclo[2.2.1]heptane
• 英文别名: exo-2-phenoxybicyclo[2.2.1]heptane；2-exo-phenoxynorbornane；exo-2-phenoxynorbornane；(1S,2S,4R)-2-phenoxybicyclo[2.2.1]heptane
• CAS: 50414-49-8；75211-13-1；50414-48-7
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: KCJZTLMEOYGMMO-MDZLAQPJSA-N

物化性质

• 沸点：
  279.5±9.0 °C(Predicted)
• 密度：
  1.077±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-exo-phenyloxybicyclo[2.2.1]heptane 在 高氯酸 作用下， 生成 双环[2.2.1]-2-庚醇 、 苯酚
  参考文献：
  名称：

  Effect of a Substituent in the Benzene Ring upon the Kinetics of Acid-Catalyzed Hydrolysis of exo-2-Norbornyl Phenyl Ether.

  摘要：

  The rate constants of hydrolysis for exo-2-norbornyl phenyl ether without substituent and with p-Me, p-Ac, m-CN, p-CN or p-NO2 group in the benzene ring were measured in concentrated perchloric acid solutions spectrophotometrically and/or by capillary GC. The effect of the substituent on the rate constants and other kinetic parameters of hydrolysis is small. The parameters are in agreement with the A-1 mechanism. The ether oxygen of the exo-epimer is much more basic than that of the endo-epimer (pK(a,exo)-pK(a,endo)approximate to 2), which causes a greater part of the exo/endo rate ratio than do the initial state energies and rate constants of the rate limiting stage, i.e. of the formation of the norbornyl cation and the substituted phenol.

  DOI：

  10.3891/acta.chem.scand.51-0515
• 作为产物：
  描述：

  降冰片烯 、 苯酚 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 1,4-二氧六环 为溶剂， 反应 18.0h， 以95%的产率得到2-exo-phenyloxybicyclo[2.2.1]heptane
  参考文献：
  名称：

  Copper(ii)-catalysed addition of O–H bonds to norbornene

  摘要：

  Cu(OTf)2是一种廉价且对空气和水分稳定的催化剂，可用于脂肪族和芳香族酸及醇对降冰片烯的O-H加成反应。

  DOI：

  10.1039/b509933a

文献信息

• Iron(III) Triflimide as a Catalytic Substitute for Gold(I) in Hydroaddition Reactions to Unsaturated Carbon-Carbon Bonds
  作者：Jose R. Cabrero-Antonino、Antonio Leyva-Pérez、Avelino Corma

  DOI：10.1002/chem.201300386

  日期：2013.6.24

  In this work it is shown that iron(III) and gold(I) triflimide efficiently catalyze the hydroaddition of a wide array of nucleophiles including water, alcohols, thiols, amines, alkynes, and alkenes to multiple CC bonds. The study of the catalytic activity and selectivity of iron(III), gold(I), and Brønsted triflimides has unveiled that iron(III) triflimide [Fe(NTf2)3] is a robust catalyst under heating

  在这项工作中表明，三氟甲磺酸铁（III）和金（I）可有效催化多种亲核试剂（包括水，醇，硫醇，胺，炔烃和烯烃）加氢成多个CC键。铁（III），金（I）和布朗斯台德三氟甲酸酯的催化活性和选择性的研究表明，三氟甲铁（III）[Fe（NTf 2）3 ]在加热条件下是一种坚固的催化剂，而金（I） ）甚至由PPh 3稳定的三氟甲酰亚胺在80°C时容易分解并释放出三氟乙二酸（HNTf 2），该三氟乙二酸可催化相应的反应，如原位19 F，15 N和311 H NMR光谱。此处给出的结果表明，两种催化剂类型均具有弱点和优势，并且彼此互补。三氟化铁（III）可以替代三氟化金（I），作为不饱和碳-碳键加氢反应的催化剂。
• REACTION OF<i>exo</i>-2-NORBORNYL AND 1-ADAMANTYL<i>p</i>-TOLUENESULFONATES WITH SODIUM PHENOXIDE IN TETRAHYDROFURAN. IONIZATION OF THE SUBSTRATES UNDER “APPARENTLY-S_N2” CONDITIONS
  作者：Ken’ichi Takeuchi、Yukari Kato、Takamasa Moriyama、Kunio Okamoto

  DOI：10.1246/cl.1981.935

  日期：1981.7.5

  exo-2-Norbornyl and 1-adamantyl tosylates react with sodium phenoxide in tetrahydrofuran via ionization, most probably through a cyclic transition state. The results call for attention in interpreting substitution reactions under “apparently-SN2” conditions.

  exo-2-Norbornyl 和 1-adamantyl tosylates 与苯酚钠在四氢呋喃中通过电离反应，最有可能通过循环过渡态。在解释“明显-SN2”条件下的取代反应时，该结果需要引起注意。
• Hydroamination and Hydroalkoxylation Catalyzed by Triflic Acid. Parallels to Reactions Initiated with Metal Triflates
  作者：Devon C. Rosenfeld、Shashank Shekhar、Akihiro Takemiya、Masaru Utsunomiya、John F. Hartwig

  DOI：10.1021/ol061174+

  日期：2006.9.1

  Intermolecular additions of the O-H bonds of phenols and alcohols and the N-H bonds of sulfonamides and benzamide to olefins catalyzed by 1 mol % of triflic acid and studies to define the relationship between these reactions and those catalyzed by metal triflates are reported. Cyclization of an alcohol containing pendant monosubstituted and trisubstituted olefins catalyzed by either triflic acid or metal triflates form products from addition to the more substituted olefin, and additions of tosylamide catalyzed by triflic acid or metal triflates form indistinguishable ratios of the two N-alkyl sulfonamides.
• Hidden Brønsted Acid Catalysis: Pathways of Accidental or Deliberate Generation of Triflic Acid from Metal Triflates
  作者：Tuan Thanh Dang、Florian Boeck、Lukas Hintermann

  DOI：10.1021/jo201631x

  日期：2011.11.18

  The generation of a hidden Bronsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF3SO3H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl2/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Bronsted acid catalyst useful for mechanistic control experiments or for synthetic applications.
• Lajunen, Martti; Himottu, Marja, Acta Chemica Scandinavica, 1989, vol. 43, # 10, p. 957 - 962
  作者：Lajunen, Martti、Himottu, Marja

  DOI：——

  日期：——