(+/-)-trans-1.2-diethoxy-cyclohexane | 93250-27-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-trans-1.2-diethoxy-cyclohexane
• 英文别名: (+/-)-trans-1.2-Diaethoxy-cyclohexan；trans-1,2-Diethoxy-cyclohexane；(1R,2R)-1,2-diethoxycyclohexane
• CAS: 93250-27-2
• 化学式: C₁₀H₂₀O₂
• 分子量: 172.268
• InChiKey: MJONXQBPXHNGIM-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  trans-1,2-cyclohexandiol 、 碘乙烷 在 sodium hydride 作用下， 生成 (+/-)-trans-1.2-diethoxy-cyclohexane
  参考文献：
  名称：

  The role of hydrogen migration in the mechanism of alcohol elimination from MH+ ions of ethers upon chemical ionization

  摘要：

  An enhanced elimination of alcohol under isobutane CI conditions, resulting in highly abundant [MH-ROH](+) ions, has been observed in several primary and secondary ethers having a tertiary beta-position (methine), as compared with those with beta-methylene. This elimination exhibits a significant degree of stereospecificity in stereoisomeric 2-methyl-1-methoxycyclohexanes 4 and 1-methoxy-trans-decalins 7, affording more abundant [MH-ROH](+) ions in the cis isomers 4c and 7tc than in their trans counterparts 4t and 7tt. These findings suggest involvement of a 1,2-hydride migration from the beta- to alpha-position in the course of the alcohol elimination from the MH+ ions of the above cis-ethers, resulting in tertiary carbocation structures. The proposed mechanism of alcohol elimination is supported by a considerable deuterium isotope effect detected in beta-deuterium-labeled cis-2-methyl-1-methoxycyclohexane and by a CID study of the structures of [MH-ROH](+) ions obtained from cis- and trans-1,2-dialkoxycyclohexanes. Ring contraction by a Meerwein-type rearrangement has also been observed in the later system. (C) 1997 by John Wiley & Sons, Ltd.No. of Figures: 16 No. of Tables: 1 No. of Refs: 22.

  DOI：

  10.1002/(sici)1096-9888(199711)32:10<1124::aid-jms570>3.0.co;2-7

文献信息

• Mercury(II) oxide/tetrafluoroboric acid-promoted vicinal hydroxy- and alkoxylation of alkenes
  作者：José Barluenga、Luisa Alonso-Cires、Pedro J. Campos、Gregorio Asensio

  DOI：10.1016/s0040-4020(01)83510-9

  日期：1984.1
• Mousseron; Granger, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1937, vol. 205, p. 327
  作者：Mousseron、Granger

  DOI：——

  日期：——
• BARLUENGA, J.;ALONSO-CIRES, L.;CAMPOS, P. J.;ASENSIO, G., TETRAHEDRON, 1984, 40, N 13, 2563-2568
  作者：BARLUENGA, J.、ALONSO-CIRES, L.、CAMPOS, P. J.、ASENSIO, G.

  DOI：——

  日期：——
• The role of hydrogen migration in the mechanism of alcohol elimination from MH+ ions of ethers upon chemical ionization
  作者：N. Morlender-Vais、A. Mandelbaum

  DOI：10.1002/(sici)1096-9888(199711)32:10<1124::aid-jms570>3.0.co;2-7

  日期：1997.11

  An enhanced elimination of alcohol under isobutane CI conditions, resulting in highly abundant [MH-ROH](+) ions, has been observed in several primary and secondary ethers having a tertiary beta-position (methine), as compared with those with beta-methylene. This elimination exhibits a significant degree of stereospecificity in stereoisomeric 2-methyl-1-methoxycyclohexanes 4 and 1-methoxy-trans-decalins 7, affording more abundant [MH-ROH](+) ions in the cis isomers 4c and 7tc than in their trans counterparts 4t and 7tt. These findings suggest involvement of a 1,2-hydride migration from the beta- to alpha-position in the course of the alcohol elimination from the MH+ ions of the above cis-ethers, resulting in tertiary carbocation structures. The proposed mechanism of alcohol elimination is supported by a considerable deuterium isotope effect detected in beta-deuterium-labeled cis-2-methyl-1-methoxycyclohexane and by a CID study of the structures of [MH-ROH](+) ions obtained from cis- and trans-1,2-dialkoxycyclohexanes. Ring contraction by a Meerwein-type rearrangement has also been observed in the later system. (C) 1997 by John Wiley & Sons, Ltd.No. of Figures: 16 No. of Tables: 1 No. of Refs: 22.