E-邻甲基苯乙酮肟 | 68251-94-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: E-邻甲基苯乙酮肟
• 英文名称: E-ortho-methylacetophenone oxime
• 英文别名: ω-(Bromomethylene)adamantane；(bromomethylidene)adamantane；2-(Bromomethylene)adamantane；bromomethyleneadamantane；bromomethylidene-adamantane；ω-Brommethylenadamantan
• CAS: 68251-94-5
• 化学式: C₁₁H₁₅Br
• 分子量: 227.144
• InChiKey: MWLCVLSMCTUPNV-WDZFZDKYSA-N

物化性质

• 熔点：
  26-28 °C
• 沸点：
  272.2±9.0 °C(Predicted)
• 密度：
  1.481±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.72
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  E-邻甲基苯乙酮肟 生成
  参考文献：
  名称：

  SASAKI, TADASHI;EGUCHI, SHOJI;TANIDA, MASAHIRO;NAKATA, FUMIYASU;ESAKI, TO+, J. ORG. CHEM., 1983, 48, N 10, 1579-1586

  摘要：

  DOI：
• 作为产物：
  描述：

  2-亚甲基金刚烷 在 吡啶 、 溴 、 sodium ethanolate 作用下， 以 乙醚 、 乙醇 、 正戊烷 为溶剂， 反应 18.0h， 生成 E-邻甲基苯乙酮肟
  参考文献：
  名称：

  三线态氧对二烯的自由基阳离子链氧化

  摘要：

  烷基化 1,3-二烯显示出通过阳离子自由基链机制氧化成内过氧化物。Diels-Alder 二聚化的空间减慢似乎是必要的；1,3-环己二烯在其1-异丙基-4-甲基衍生物产生96%蛔虫收率的条件下仅产生二聚体。阳离子自由基链条件比单线态氧反应更能耐受空间拥挤，因为 4,4'-双高金刚烯基产生了 84% 的内过氧化物，而单线态氧产生了几种产物的混合物。从二金刚烷基乙烷中未观察到氧化产物，其在空间上被禁止呈现 s-cis 构象。

  DOI：

  10.1021/ja00278a022

文献信息

• Synthesis of adamantane derivatives. 61. Convenient generation of adamantylidenecarbene from (bromomethylene)adamantane. An efficient method of adamantylidenecyclopropanation
  作者：Tadashi Sasaki、Shoji Eguchi、Masahiro Tanida、Fumiyasu Nakata、Toshiyuki Esaki

  DOI：10.1021/jo00158a002

  日期：1983.5
• Kostikov, R. R.; Grishina, E. N.; Slobodin, Ya. M., Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, p. 1298 - 1306
  作者：Kostikov, R. R.、Grishina, E. N.、Slobodin, Ya. M.

  DOI：——

  日期：——
• Crown ether catalyzed generation of adamantylidene carbene from ω-bromomethyleneadamantane and potassium -butoxide
  作者：Tadashi Sasaki、Shoji Eguchi、Fumiyasu Nakata

  DOI：10.1016/s0040-4039(01)94731-8

  日期：1978.1
• A new entry of highly nucleophilic CHBr3–TiCl4–Mg system for the stereoselective synthesis of 1-alkenyl bromides
  作者：Yeshwant Ramchandra Bhorge、Su-Haur Chang、Cheng-Ta Chang、Tu-Hsin Yan

  DOI：10.1016/j.tet.2012.03.123

  日期：2012.6

  This TiCl4-Mg promoted coupling of CHBr3 with various aldehydes and ketones, especially in sterically hindered or enolizable ketones, provides a simple, practical, and stereoselective carbonyl-bromomethylenation leading primarily to (E)-vinyl bromides. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.
• Preparation and carbon 13 NMR spectroscopic study of the 2-(adamantylidenemethyl)-2-adamantyl and 2-adamantylidene-1,1-dicyclopropylethyl cations
  作者：George A. Olah、V. Prakash Reddy、Joseph Casanova、G. K. Surya Prakash

  DOI：10.1021/jo00050a014

  日期：1992.11

  2-(Adamantylidenemethyl)-2-adamantyl cation (5) was prepared by ionization of 2-(adamantylidenemethyl)-2-adamantanol (9) in FSO3H/SO2ClF or neat FSO3H at -78-degrees-C. In spite of its high inherent steric strain, carbocation 5 is stable up to 80-degrees-C. Its rotational barrier was estimated to be 16.8 kcal/mol on the basis of the coalescence temperature of the C-13 NMR signals of its diastereomeric beta-methylene carbons, which is in agreement with a DELTAH(double dagger) value of 16.5 kcal/mol calculated by MNDO. Similarly, 2-adamantylidene-l,l-dicyclopropylethyl cation (6) was prepared by the ionization of 1,1-dicyclopropyl-2-(2-hydroxy-2-adamantyl)ethanol (12) in SbF5-FSO/SO2ClF or FSO3H/SO2ClF. Carbocation 6 shows a rotational barrier of less than 5 kcal/mol. The small rotational barrier in 6 is interpreted as due to the positive charge stabilizing influence of the adjacent cyclopropyl groups resulting in an unsymmetrically charge-delocalized allylic cation.