2-Bromoprop-2-enyl cyclohex-2-enyl ether | 106202-75-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2-Bromoprop-2-enyl cyclohex-2-enyl ether
• 英文别名: Cyclohexene, 3-[(2-bromo-2-propenyl)oxy]-；3-(2-bromoprop-2-enoxy)cyclohexene
• CAS: 106202-75-9
• 化学式: C₉H₁₃BrO
• 分子量: 217.106
• InChiKey: JAXYXFORGSGTTL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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-Bromoprop-2-enyl cyclohex-2-enyl ether 在 叔丁基过氧化氢 、 六甲基磷酰三胺 、 bis(acetylacetonate)oxovanadium 、 lithium di(n-butyl)cuprate 、 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 、 氯仿 为溶剂， 反应 33.0h， 生成
  参考文献：
  名称：

  eriolanin的一种方法。反式1,3-二羟基环己烷的α-亚甲基内酯的合成

  摘要：

  讨论了一种新的α-亚甲基内酯的合成方法，该方法结合了带有乙烯基阴离子的分子内环氧化物开口。

  DOI：

  10.1016/s0040-4039(00)84097-6
• 作为产物：
  描述：

  2-溴-2-丙烯-1-醇 、 2-环己烯醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 18.0h， 以81%的产率得到2-Bromoprop-2-enyl cyclohex-2-enyl ether
  参考文献：
  名称：

  eriolanin的一种方法。反式1,3-二羟基环己烷的α-亚甲基内酯的合成

  摘要：

  讨论了一种新的α-亚甲基内酯的合成方法，该方法结合了带有乙烯基阴离子的分子内环氧化物开口。

  DOI：

  10.1016/s0040-4039(00)84097-6

文献信息

• Generation and Mesolysis of PhSeSiR₃]^•-:  Mechanistic Studies by Laser Flash Photolysis and Application for Bimolecular Group Transfer Radical Reactions
  作者：Ganesh Pandey、K. S. Sesha Poleswara Rao、D. K. Palit、J. P. Mittal

  DOI：10.1021/jo972345e

  日期：1998.6.1

  The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET promoted reductive activation of selenosilane la to its radical anion la(-.). PET activation of la is achieved through a photosystem comprising a light-absorbing electron-rich aromatic (ERA), such as DMN or DMA, as an electron donor and ascorbic acid as a co-oxidant. The evidence for the ET from excited singlet states of DMN as well as DMA to la is suggested by estimating negative Delta G(et) (-51 and -43.46 kcal mol(-1), respectively) values and nearly diffusion-controlled fluorescence quenching rate constants (k(q)TR) 0.36 x 10(10) M-1 s(-1) and 0.28 x 10(10) M-1 s(-1), respectively, from time-resolved fluorescence quenching study. The transient absorption spectra of DMN.+, DMA(.+), and la(.-) are obtained initially by pulse radiolysis in order to correlate the time-resolved absorption spectral data. Laser flash photolysis studies in the nanosecond time domain have confirmed the generation of la(.-), DMN.+, and DMA(.+), supporting the participation of the triplet state of DMN or DMA in the ET reaction. Mesolytic cleavage of 1a(.-) produced a silyl radical and a phenyl selenide anion. The preparative PET activation of la in acetonitrile in the presence of DMN or DMA leads to the formation of 5 and 6, confirming the fragmentation pattern of la(.-). The overall ET rate constants (K-r(DMN) = 0.99 x 10(10) M-1 s(-1) and k(r)(DMA) = 1.62 x 10(10) M-1 s(-1)) and limiting quantum yields (phi(lim)DMN) = 0.034 and phi(lim)(DMA) = 0.12) are estimated from the inverse plot (1/[la] vs 1/phi(dis)) Obtained by measuring the dependence of photodissociation quantum yields of la at its maximum concentration in the presence of DMN or DMA. Silicon-centered radical species generated from the mesolysis of la(.-) are utilized for initiating a radical reaction by the abstraction of halogen atom from -C-X (X = Cl, Br) bonds, while PhSe- terminates the radical sequences via PhSeSePh. This concept is successfully applied for the bimolecular group transfer (BMGT) radical reactions and intermolecular radical chain addition reactions.
• Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Maria Luisa Navacchia

  DOI：10.1021/jo00128a013

  日期：1995.11

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.
• Pandey, Ganesh; Rao, K.S. Sesha Poleshwar, Angewandte Chemie, 1995, vol. 107, # 23/24, p. 2934 - 2935
  作者：Pandey, Ganesh、Rao, K.S. Sesha Poleshwar

  DOI：——

  日期：——
• An approach to eriolanin. Synthesis of α-methylene lactones of trans-1,3-dihydroxycyclohexanes
  作者：Marie E. Krafft

  DOI：10.1016/s0040-4039(00)84097-6

  日期：1986.1

  A new synthesis of α-methylene lactones is discussed which incorporates an intramolecular epoxide opening with a vinyl anion.

  讨论了一种新的α-亚甲基内酯的合成方法，该方法结合了带有乙烯基阴离子的分子内环氧化物开口。