1-Chloro-3,3-dimethyl-2-oxobicyclo<2.2.2>heptane | 37611-37-3

• 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: 1-Chloro-3,3-dimethyl-2-oxobicyclo<2.2.2>heptane
• 英文别名: 1-chloro-3,3-dimethylbicyclo[2.2.1]heptan-2-one；1-chloro-3,3-dimethyl-norbornan-2-one；α-Chlor-camphenilon；4-Chlor-2.2-dimethyl-bicyclo-[1.2.2]-heptanon-(3)；1-Chlor-3,3-dimethyl-norbornan-2-on
• CAS: 37611-37-3
• 化学式: C₉H₁₃ClO
• 分子量: 172.655
• InChiKey: OCKZCQHGHILAQG-UHFFFAOYSA-N

物化性质

• 沸点：
  236.1±13.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Chloro-3,3-dimethyl-2-oxobicyclo<2.2.2>heptane 、 三苯基膦 在 sodium 、 叔丁醇 作用下， 以 氨 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  卤硼硼烷和含氧取代衍生物与不同阴离子的反应通过电子转移机理进行；稳定基团中的氧化还原催化† ‡

  摘要：

  的反应 2溴-， 2-氯降冰片烷， 3-氯降冰片-2-一 和 3-溴樟脑 和 我3锡−，PH 2 P-或PHS -由S进行了研究离子RN在液体1机构氨 或者 二甲基亚砜。结果表明，具有羰基的底物促进电子转移反应，这在不存在这种基团的情况下受到阻碍。然而，当通过结合使形成的自由基稳定时，偶联反应降低，导致还原产物随之增加。理论研究基于涉及还原裂解的机制解释了所观察到的反应性，该还原裂解是π-σ相互作用的函数。

  DOI：

  10.1039/b9nj00503j
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 臭氧 、 溶剂黄146 作用下， 生成 1-Chloro-3,3-dimethyl-2-oxobicyclo<2.2.2>heptane
  参考文献：
  名称：

  Meerwein; Wortmann, Justus Liebigs Annalen der Chemie, 1924, vol. 435, p. 194 Anm.1

  摘要：

  DOI：

文献信息

• Intramolecular Electron Transfer Reactions Catalyzed by .alpha.-Oxo and .beta.-Oxo Substituents in the 1-Chlorobicyclo[2.2.1]heptane System
  作者：Andres E. Lukach、David G. Morris、Ana N. Santiago、Roberto A. Rossi

  DOI：10.1021/jo00109a035

  日期：1995.2

  Efficient intramolecular ET catalysis in S(RN)1 reactions was observed when a carbonyl group is present in 1-chlorobicyclo[2.2.1]heptane in the alpha or beta position. 1-Chloro-3,3-dimethyl-2-oxobicyclo[2.2.1]heptane (1) and 4-chloro-1,7,7-trimethyl-2-oxobicyclo[2.2.1]heptane (4) reacted with diphenylphosphide ion (Ph(2)P(-)) as nucleophile in liquid ammonia under photostimulation to give the substitution products in good yields, together with very small amounts of the reduction product. The substitution products were not observed in dark conditions, and the photostimulated reactions were inhibited by p-dinitrobenzene. These reactions are proposed to proceed via the S(RN)1 mechanism. In competition experiments, the reactivity ratio of 1 to 4 was 2.8, whereas the ratio of 1-chloro-3,3-dimethyl-2-oxobicyclo[2.2.2]octane (8) to 4 was 1.1. On the other hand, 1-chloro-2-methylene-3, 3-dimethylbicyclo[2.2.1]heptane (7) was unreactive under these experimental conditions. It then seems to follow that when there is a carbonyl group in these bicyclic compounds, in the a or beta position, they react by the S(RN)1 mechanism, and the overall reactivity is similar, but when the C=O is replaced by a C=C, the substrate did not react in these experimental conditions. These results are in agreement with MO calculations, in which the LUMO of compounds 1, 4, and 8 belongs to the pi* MO of the C=O group, with similar energies, and is lower than the pi* MO of 7.
• Meerwein; Wortmann, Justus Liebigs Annalen der Chemie, 1924, vol. 435, p. 194 Anm.1
  作者：Meerwein、Wortmann

  DOI：——

  日期：——
• Reactions of halonorbornane and oxo-substituted derivatives with different anions by the electron transfer mechanism; redox catalysis in stabilized radicals
  作者：Jorge G. Uranga、Ana N. Santiago

  DOI：10.1039/b9nj00503j

  日期：——

  3-chloronorbornan-2-one and 3-bromocamphor with Me3Sn−, Ph2P− or PhS− ions were studied by an SRN1 mechanism in liquid ammonia or DMSO. The results show that substrates having a carbonyl group facilitate electron transfer reactions, which are impeded in the absence of such a group. However, when the free radical formed is stabilized by conjugation, the coupling reaction decreases, causing a concomitant increase

  的反应 2溴-， 2-氯降冰片烷， 3-氯降冰片-2-一 和 3-溴樟脑 和 我3锡−，PH 2 P-或PHS -由S进行了研究离子RN在液体1机构氨 或者 二甲基亚砜。结果表明，具有羰基的底物促进电子转移反应，这在不存在这种基团的情况下受到阻碍。然而，当通过结合使形成的自由基稳定时，偶联反应降低，导致还原产物随之增加。理论研究基于涉及还原裂解的机制解释了所观察到的反应性，该还原裂解是π-σ相互作用的函数。