7,7-dibromoborbornane | 51689-30-6

• 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: 7,7-dibromoborbornane
• 英文别名: 7,7-dibromonorbornane；Dibromonorbornane；7,7-dibromobicyclo[2.2.1]heptane
• CAS: 51689-30-6
• 化学式: C₇H₁₀Br₂
• 分子量: 253.964
• InChiKey: WQLOPWOVROOXQQ-UHFFFAOYSA-N

物化性质

• 沸点：
  229.0±13.0 °C(Predicted)
• 密度：
  1.918±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  7,7-dibromoborbornane 在 magnesium 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 7-norbornylidene-7-norbornane
  参考文献：
  名称：

  Electrophilic Bromination of 7-Norbornylidene-7'-Norbornane. The Observation of an Unusually Large Inverse Deuterium Kinetic Isotope Effect

  摘要：

  The bromination of 7-norbornylidene-7'-norbornane (1) and its perdeuterated analogue (2) was studied in HOAc and MeOH by investigating the reaction kinetics and product distributions as a function of added [Br-]. In all cases there is a significant inverse deuterium kinetic isotope effect on the bromination rate constant (k(g)) which, in HOAc, is k(g)(2/1) 1.56 and 1.83 at [Br-] = 0 and 0.04 M, respectively. Added Br- causes a significant rate retardation which indicates the intervention of a reversibly formed bromonium ion intermediate. Product studies indicate the formation of four products, a normal dibromide and beta-bromo solvate and two that arise from capture of an alpha-bromo cation formed from a Wagner-Meerwein rearrangement of the first-formed bromonium ion. In HOAc, added [Br-] leads to an increase in the amount of the normal dibromide at the expense of the solvent-incorporated and rearranged products. In MeOH, dibromide is never an important product at any [Br-] investigated, the two major isolated products being the normal methoxy bromide and rearranged ketone. Quantitative analyses of the products formed from bromination of 1 and 2 in HOAc as a function of [Br-] indicate little difference in the product partitioning that is attributable to the presence of H or D. A unified mechanism that accommodates all the data is presented.

  DOI：

  10.1021/ja00139a009
• 作为产物：
  描述：

  7-norbornanone 在 五溴化磷 作用下， 反应 0.75h， 以67%的产率得到7,7-dibromoborbornane
  参考文献：
  名称：

  Electrophilic Bromination of 7-Norbornylidene-7'-Norbornane. The Observation of an Unusually Large Inverse Deuterium Kinetic Isotope Effect

  摘要：

  The bromination of 7-norbornylidene-7'-norbornane (1) and its perdeuterated analogue (2) was studied in HOAc and MeOH by investigating the reaction kinetics and product distributions as a function of added [Br-]. In all cases there is a significant inverse deuterium kinetic isotope effect on the bromination rate constant (k(g)) which, in HOAc, is k(g)(2/1) 1.56 and 1.83 at [Br-] = 0 and 0.04 M, respectively. Added Br- causes a significant rate retardation which indicates the intervention of a reversibly formed bromonium ion intermediate. Product studies indicate the formation of four products, a normal dibromide and beta-bromo solvate and two that arise from capture of an alpha-bromo cation formed from a Wagner-Meerwein rearrangement of the first-formed bromonium ion. In HOAc, added [Br-] leads to an increase in the amount of the normal dibromide at the expense of the solvent-incorporated and rearranged products. In MeOH, dibromide is never an important product at any [Br-] investigated, the two major isolated products being the normal methoxy bromide and rearranged ketone. Quantitative analyses of the products formed from bromination of 1 and 2 in HOAc as a function of [Br-] indicate little difference in the product partitioning that is attributable to the presence of H or D. A unified mechanism that accommodates all the data is presented.

  DOI：

  10.1021/ja00139a009

文献信息

• Preparation and some properties of 7,7-dilithionorbornane
  作者：Cornelis P. Vlaar、Gerhard W. Klumpp

  DOI：10.1016/0040-4039(91)80659-t

  日期：1991.6

  7,7-Dilithionorbornane 4a is formed from 7,7-dibromonorbornane 4b by reduction with 4,5 equiv of lithium p,p′-di-tert-butylbiphenyl at −100°C,at which temperature it adds to ethylene. On warming it rearranges to 1-1ithio-5-(2-lithioethyl)cyclopentene 5.

  7,7- Dilithionorbornane 4A是从7,7- dibromonorbornane形成图4b通过还原4,5-当量锂的P，P ' -二-叔-butylbiphenyl在-100℃，在此温度将其添加到乙烯。在加热时，它重排成1-1ithio-5-（2-lithioethyl）cyclopentene 5。
• Oxidative coupling of 7,7-dilithionorbornane; 7,7′-dilithio-7,7′-dinorbornyl, a new vic-dilithioalkane prone to a new mode of decomposition
  作者：Cornelis P. Vlaar、Gerhard W. Klumpp

  DOI：10.1016/s0040-4039(00)60647-0

  日期：1993.9

  7,7-Dilithionorbornane reacts with butyl halides at -100-degrees-C to give 7,7'-dilithio-7,7'-dinorbornyl (30%), which is easily oxidized to 7.7-dinorbornylidene.
• Electrophilic Bromination of 7-Norbornylidene-7'-Norbornane. The Observation of an Unusually Large Inverse Deuterium Kinetic Isotope Effect
  作者：H. Slebocka-Tilk、S. Motallebi、R. W. Nagorski、P. Turner、R. S. Brown、R. McDonald

  DOI：10.1021/ja00139a009

  日期：1995.8

  The bromination of 7-norbornylidene-7'-norbornane (1) and its perdeuterated analogue (2) was studied in HOAc and MeOH by investigating the reaction kinetics and product distributions as a function of added [Br-]. In all cases there is a significant inverse deuterium kinetic isotope effect on the bromination rate constant (k(g)) which, in HOAc, is k(g)(2/1) 1.56 and 1.83 at [Br-] = 0 and 0.04 M, respectively. Added Br- causes a significant rate retardation which indicates the intervention of a reversibly formed bromonium ion intermediate. Product studies indicate the formation of four products, a normal dibromide and beta-bromo solvate and two that arise from capture of an alpha-bromo cation formed from a Wagner-Meerwein rearrangement of the first-formed bromonium ion. In HOAc, added [Br-] leads to an increase in the amount of the normal dibromide at the expense of the solvent-incorporated and rearranged products. In MeOH, dibromide is never an important product at any [Br-] investigated, the two major isolated products being the normal methoxy bromide and rearranged ketone. Quantitative analyses of the products formed from bromination of 1 and 2 in HOAc as a function of [Br-] indicate little difference in the product partitioning that is attributable to the presence of H or D. A unified mechanism that accommodates all the data is presented.