(+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-ene | 63025-72-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-ene
• 英文别名: dehydrocineole；(1RS,4SR)-1,8-epoxy-p-menth-2-ene；(1RS,4SR)-1,8-Epoxy-p-menth-2-en；(1R,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-ene
• CAS: 63025-72-9；66113-06-2；88444-55-7；92760-25-3
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: LOOYOTLEOHYYOV-SCZZXKLOSA-N

物化性质

• 沸点：
  180.0±29.0 °C(Predicted)
• 密度：
  0.948±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-ene 在 铂 氢气 作用下， 生成 1,8-cineole
  参考文献：
  名称：

  Synthesis of dehydrocineole, a new monoterpene from the acarid mite, (arachnida: acari)

  摘要：

  DOI：

  10.1016/s0040-4039(01)91066-4
• 作为产物：
  描述：

  1,8-cineole 在 chromium(VI) oxide 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 乙酸酐 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 65.5h， 生成 (+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-ene
  参考文献：
  名称：

  Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system

  摘要：

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00313-0

文献信息

• Carbonyl transposition and regio- and stereo-specific syntheses of new alcohols, amino-alcohols, and ketones in the monoterpenoid 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane
  作者：Francesco Bondavalli、Pietro Schenone、Angelo Ranise、Silvia Lanteri

  DOI：10.1039/p19800002626

  日期：——

  An efficient transposition of carbonyl group R1–CO–CH2–R2→ R1–CH2–CO–R2 in the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane system was carried out via hydroboration–oxidation of 6-dialkylamino-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-enes (3a–c), which gave regio- and stereo-specifically 6-cis-dialkylamino-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-trans-ols (4a–c) in high yield. Cope reaction of the

  在1,3,3-三甲基-2-氧杂双环[2.2.2]辛烷体系中进行了羰基基团R 1 –CO–CH 2 –R 2 → R 1 –CH 2 –CO–R 2的有效置换。通过氢硼化-氧化6-二烷基氨基-1,3,3-三甲基-2-恶二环[2.2.2]辛-5-烯（3a–c），得到区域和立体特异性的6-顺式-二烷基氨基- 1,3,3-三甲基-2-氧杂双环[2.2.2] octan -5-反式-ols（4a–c）高产率。应对氮的反应由氨基醇（4b）与过氧化氢制得的一氧化碳（5b）生成1,3,3-三甲基-2-氧杂双环[2.2.2]辛基-5-酮（6），这是其另一种可能的异构体众所周知的1,3,3-三甲基-2-氧杂双环[2.2.2] octan-6-one（1b）。酮（6）还由1,3,3-三甲基-2-氧杂双环[2.2.2]辛-5-烯（2）通过其反式环氧化物（11），氢化铝锂在160-165的还原度制得。其℃得到立体和区域特异性的1
• Gandini, Gazzetta Chimica Italiana, 1934, vol. 64, p. 302,310
  作者：Gandini

  DOI：——

  日期：——
• Gandini, Gazzetta Chimica Italiana, 1934, vol. 64, p. 118,123, 125, 129, 130
  作者：Gandini

  DOI：——

  日期：——
• Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system
  作者：Frederick A. Luzzio、Damien Y. Duveau

  DOI：10.1016/s0957-4166(02)00313-0

  日期：2002.6

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of dehydrocineole, a new monoterpene from the acarid mite, (arachnida: acari)
  作者：F.O. Ayorinde、J.W. Wheeler、R.M. Duffield

  DOI：10.1016/s0040-4039(01)91066-4

  日期：1984.1