dimethyl 2-(dicyclohexylamino)-2-methylpropane-1,3-dioate | 1135530-67-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 2-(dicyclohexylamino)-2-methylpropane-1,3-dioate
• 英文别名: Dimethyl 2-(dicyclohexylamino)-2-methylpropanedioate
• CAS: 1135530-67-4
• 化学式: C₁₈H₃₁NO₄
• 分子量: 325.448
• InChiKey: QKCVUTTXIUBWQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(dicyclohexylamino)-2-methylpropane-1,3-dioate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以66.2%的产率得到2-(dicyclohexylamino)-2-methylpropane-1,3-diol
  参考文献：
  名称：

  Trialkylamines More Planar at Nitrogen Than Triisopropylamine in the Solid State

  摘要：

  A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1-piperidinyl)propane-1,3-diol (10) may be prepared easily. Examination of amines of this type by X-ray crystallography reveals nearly planar nitrogens. Indeed, they are all more planar than the nitrogen of triisopropylamine, which had long been thought to be perfectly planar, but which is in fact very slightly pyramidal. The distance (h) of the nitrogen of triisopropylamine to the plane defined by the three carbons to which it is bonded is 0.28-0.29 angstrom. In 8, by comparison, h is 0.185 angstrom. A qualitative orbital interaction explanation is proposed to rationalize the tendency of nitrogen to planarize when attached to the 1,3-dihydroxy-2-propyl group. Cyclic voltammetric measurements of nitrogen one-electron oxidation of the nearly planar trialkylamines revealed no correlation between E-1/2(ox) and degree of planarity.

  DOI：

  10.1021/jo802086h
• 作为产物：
  描述：

  dimethyl 2-(dicyclohexylamino)propanedioate 、 碘甲烷 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 0.5h， 以74%的产率得到dimethyl 2-(dicyclohexylamino)-2-methylpropane-1,3-dioate
  参考文献：
  名称：

  Trialkylamines More Planar at Nitrogen Than Triisopropylamine in the Solid State

  摘要：

  A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1-piperidinyl)propane-1,3-diol (10) may be prepared easily. Examination of amines of this type by X-ray crystallography reveals nearly planar nitrogens. Indeed, they are all more planar than the nitrogen of triisopropylamine, which had long been thought to be perfectly planar, but which is in fact very slightly pyramidal. The distance (h) of the nitrogen of triisopropylamine to the plane defined by the three carbons to which it is bonded is 0.28-0.29 angstrom. In 8, by comparison, h is 0.185 angstrom. A qualitative orbital interaction explanation is proposed to rationalize the tendency of nitrogen to planarize when attached to the 1,3-dihydroxy-2-propyl group. Cyclic voltammetric measurements of nitrogen one-electron oxidation of the nearly planar trialkylamines revealed no correlation between E-1/2(ox) and degree of planarity.

  DOI：

  10.1021/jo802086h

文献信息

• Trialkylamines More Planar at Nitrogen Than Triisopropylamine in the Solid State
  作者：Minmin Yang、Thomas Albrecht-Schmitt、Vince Cammarata、Peter Livant、David S. Makhanu、Richard Sykora、Wei Zhu

  DOI：10.1021/jo802086h

  日期：2009.4.3

  A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1-piperidinyl)propane-1,3-diol (10) may be prepared easily. Examination of amines of this type by X-ray crystallography reveals nearly planar nitrogens. Indeed, they are all more planar than the nitrogen of triisopropylamine, which had long been thought to be perfectly planar, but which is in fact very slightly pyramidal. The distance (h) of the nitrogen of triisopropylamine to the plane defined by the three carbons to which it is bonded is 0.28-0.29 angstrom. In 8, by comparison, h is 0.185 angstrom. A qualitative orbital interaction explanation is proposed to rationalize the tendency of nitrogen to planarize when attached to the 1,3-dihydroxy-2-propyl group. Cyclic voltammetric measurements of nitrogen one-electron oxidation of the nearly planar trialkylamines revealed no correlation between E-1/2(ox) and degree of planarity.