7,7-二甲基二环[2.2.1]庚烷-4-醇 | 22463-27-0

• 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
• 中文名称: 7,7-二甲基二环[2.2.1]庚烷-4-醇
• 英文名称: 1-apocamphanol
• 英文别名: 1-hydroxy-7.7-dimethyl-norbornane；1-Hydroxy-7.7-dimethyl-bicyclo[2.2.1]heptan；1-Hydroxy-7.7-dimethyl-norbornan；7.7-Dimethyl-norbornanol-(1)；7,7-Dimethylnorbornan-1-ol；7,7-Dimethylbicyclo[2.2.1]heptan-1-ol
• CAS: 22463-27-0
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: ZFVYXCUQKKZDMM-UHFFFAOYSA-N

物化性质

• 熔点：
  161-162 °C
• 沸点：
  190.7±8.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 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：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  7,7-二甲基二环[2.2.1]庚烷-4-醇 在 三氯化铝 、 磺酰氯 作用下， 生成 1-Phenyl-7,7-dimethylnorbornan
  参考文献：
  名称：

  Takeuchi,K. et al., Journal of the Chemical Society. Perkin transactions I, 1976, p. 2205 - 2206

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-(+)-酮基蒎酸 在 palladium on activated charcoal 氢气 作用下， 生成 7,7-二甲基二环[2.2.1]庚烷-4-醇
  参考文献：
  名称：

  Reactions of apotricyclyl, apocamphor, and apobornenyl chloroformates with silver(I). Generation and aromatic substitution of a bridgehead radical and a bridgehead cation

  摘要：

  DOI：

  10.1021/ja00827a020

文献信息

• The reaction between acyl halides and alcohols: Alkyl halide vs. Ester formation
  作者：Paolo Strazzolini、Angelo G. Giumanini、Giancarlo Verardo

  DOI：10.1016/s0040-4020(01)80747-x

  日期：1994.4

  therefore, ester formation practically confined to a triggering role. But, in those cases where the cation is less easily formed, ester formation was favoured and, consequently, became the necessary elementary step towards alkyl halide formation. This final product, on the other hand, might be extremely slow to form in an SN2 reaction between the protonated ester function and the halide ion. In these hnstances

  在酰基卤和醇之间的反应中，热力学上有利的产物是游离羧酸和烷基卤。最初的反应通常是形成酯和HHal。当该醇非常容易被HHal质子化时产生烷基阳离子时，形成的H 2 O表现出超活性，并且与该醇成功竞争了酰基卤的制备，因此，酯的形成实际上局限于触发作用。但是，在那些阳离子不易形成的情况下，有利于酯的形成，因此成为形成卤代烷的必要的基本步骤。另一方面，最终产品在S N中的形成速度可能非常慢2质子化的酯官能团与卤离子之间的反应。因此，在这些情况下，以及在碱性溶剂竞争HHal质子的情况下，酯都是最终产物。α-羟基，α-苯基苯乙酸（2y）给出了上述虚线所示的一个显着例外，它似乎通过季中间体（E）进行了直接的氯-羟基交换，最后塌陷为α-氯- α-苯基苯乙酸（4y）。在严格相似的条件下，使用CH 2 Cl 2作为溶剂比较了不同的系统。测试了约28种不同的底物与AcCl（1a）的反应，而八种酰基卤（1）对（R
• Hypoiodite reaction: the decomposition of oxalic acid half-esters
  作者：K. Bartel、A. Goosen、A. Scheffer

  DOI：10.1039/j39710003766

  日期：——

  Alkyl half-esters of oxalic acid photolysed with mercury(II) oxide–iodine reagent gave mainly dialkyl oxalates. 1-Apocamphyl hydrogen oxalate gave, in addition to the diester, 1-apocamphyl iodide. 9-Triptycyl hydrogen oxalate gave 9-triptycyl iodoformate, which was thermally decomposed to 9-iodotriptycene and with silver tetrafluoroborate gave 9-triptycyl fluoroformate. We suggest that diester formation

  草酸的烷基半酯与氧化汞（II）-碘试剂光解后，生成的主要是草酸二烷基酯。除二酯外，1-阿朴茶酸草酸氢盐还产生了1-阿朴茶酸碘化物。9-三苯甲基草酸氢酯产生9-三苯甲基碘甲酸酯，将其热分解成9-碘三苯并噻吩，并与四氟硼酸银一起产生9-三苯甲基氟甲酸酯。我们建议通过中间烷氧基羰基基团的偶联发生二酯形成。
• Decomposition of diacyl peroxide—V
  作者：S. Oae、K. Fujimori、Y. Uchida

  DOI：10.1016/s0040-4020(01)93854-2

  日期：1972.1

  Specifically 18O-labeled benzoyl 1-apocamphyl carbonate which corresponds to the carboxy-inversion product of 1-apocamphoryl benzoyl peroxide was synthesized and heated in CCl4. The two carbonyl oxygen atoms and an etheral oxygen atom sandwiched between two carbonyl carbon atoms in benzoyl 1-apocamphyl carbonate were completely scrambled. Heating of 18O-labeled benzoyl 1-apocamphyl carbonate with an

  具体地，合成18个O-标记的碳酸苯甲酰基1-脱羧基碳酸酯，其对应于1-脱羧甲基苯甲酰过氧化物的羧基转化产物，并在CCl 4中加热。苯甲酰基1-基己糖碳酸酯中的两个羰基氧原子和一个夹在两个羰基碳原子之间的醚氧原子被完全打乱。在CCl 4中用等摩尔量的苯甲酸加热18 O-标记的苯甲酰基1-阿朴樟脑碳酸酯，定量得到1-apphomphanol，CO 2和苯甲酸酐。根据这些产品的18 O分析和其他数据，提出了一个分子内机理，该机理认为氧在苯甲酰1-载茶树碳酸酯中的加扰作用。
• Reinvestigation of the SNi reaction. The ionization of chlorosulfites
  作者：Peter R. Schreiner、Paul v. R. Schleyer、Richard K. Hill

  DOI：10.1021/jo00062a028

  日期：1993.5

  The decomposition of alkyl chlorosulfites (ROSOCl) has been investigated both computationally and experimentally. Semiempirical (AM1 and PM3) as well as ab initio (HF/3-21G(*), HF/6-31G*, and MP2(full)/6-31G*//MP2(full)/6-31G*) methods were employed, and the results were confirmed experimentally by NMR spectroscopy. The computations indicated that certain alkyl sulfinyl cations (ROSO+) are stable and might be involved in the decomposition of chlorosulfites. Detection of these ions by H-1 and C-13 NMR spectroscopy in polar solvents such as acetone-d6 and acetonitrile-d3 as well as kinetic studies allowed important conclusions to be drawn about the mechanistic details of the S(N)i reaction. We conclude that primary alkyl chlorosulfites ionize to yield a sulfinyl cation (ROSO+) and Cl-, whereas tertiary chlorosulfites preferentially give a carbenium ion and a chlorosulfinyl anion (OSOCl-). The generation of these ion pairs is facilitated in polar solvents where the rates of decomposition of chlorosulfites are largely accelerated. The decomposition of neopentyl chlorosulfite without rearrangement and the substitution at the bridgehead position of 7,7-dimethylbicyclo[2.2.1]-heptyl 1-chlorosulfite show that the loss Of SO2 from ROSO+ must be accompanied by the attack of the chloride ion from the front side.
• Reactions of chloroformates with silver fluoro salts
  作者：Peter Beak、Ronald J. Trancik、David A. Simpson

  DOI：10.1021/ja01046a023

  日期：1969.8