1-methoxy-3,5-dimethylbenzene-2,4,6-d3 | 1009736-60-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-methoxy-3,5-dimethylbenzene-2,4,6-d3
• CAS: 1009736-60-0
• 化学式: C₉H₁₂O
• 分子量: 139.17
• InChiKey: JCHJBEZBHANKGA-WVALGTIDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.31
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-methoxy-3,5-dimethylbenzene-2,4,6-d3 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 乙腈 为溶剂， 反应 16.0h， 生成 1-bromo-4-methoxy-3,5-dimethylbenzene-3,5-d2
  参考文献：
  名称：

  Steric Isotope Effects Gauged by the Bowl-Inversion Barrier in Selectively Deuterated Pentaarylcorannulenes

  摘要：

  Motivated by a greater bowl depth and barrier to bowl inversion in sym-1,3,5,7,9-pentamanisylcorannulene compared to corannulene, an experimental plan is developed to measure the effective hydrogen/deuterium steric kinetic isotope effect (KIE). Symmetry arguments are used to design orthogonal isotope labeling patterns so that the barrier for the CD3 compound can be measured in the presence of the CH3 compound. This scheme eliminates the differential uncertainty in the temperature measurement by allowing both barriers to be measure in the same sample, which in turn reduces the error in determining the differential barrier. Ab initio computations corroborate the structure and isotope effect found experimentally. The predicted and determined steric KIE at 250 K is 1.08 (modified QUIVER at M06-2X/ cc-pVDZ) and 1.22 +/- 0.06 (VT-NMR), respectively. The results stem from differences in zero-point energy of the CH and CD motions; however, the phenomenology makes the CD3 group appear effectively "stickier" than CH3. The more the C-H center dot center dot center dot X interaction steepens the well, the "stickier" C-D should appear to be relative to C-H-an important consideration for molecular recognition and one supported by stronger binding constants for deuterated substrates.

  DOI：

  10.1021/ja073052y
• 作为产物：
  描述：

  顺-3-氯二氢-5-苯基呋喃-2(3H)-酮 、 碘甲烷 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 33.0h， 生成 1-methoxy-3,5-dimethylbenzene-2,4,6-d3
  参考文献：
  名称：

  Steric Isotope Effects Gauged by the Bowl-Inversion Barrier in Selectively Deuterated Pentaarylcorannulenes

  摘要：

  Motivated by a greater bowl depth and barrier to bowl inversion in sym-1,3,5,7,9-pentamanisylcorannulene compared to corannulene, an experimental plan is developed to measure the effective hydrogen/deuterium steric kinetic isotope effect (KIE). Symmetry arguments are used to design orthogonal isotope labeling patterns so that the barrier for the CD3 compound can be measured in the presence of the CH3 compound. This scheme eliminates the differential uncertainty in the temperature measurement by allowing both barriers to be measure in the same sample, which in turn reduces the error in determining the differential barrier. Ab initio computations corroborate the structure and isotope effect found experimentally. The predicted and determined steric KIE at 250 K is 1.08 (modified QUIVER at M06-2X/ cc-pVDZ) and 1.22 +/- 0.06 (VT-NMR), respectively. The results stem from differences in zero-point energy of the CH and CD motions; however, the phenomenology makes the CD3 group appear effectively "stickier" than CH3. The more the C-H center dot center dot center dot X interaction steepens the well, the "stickier" C-D should appear to be relative to C-H-an important consideration for molecular recognition and one supported by stronger binding constants for deuterated substrates.

  DOI：

  10.1021/ja073052y

文献信息

• Steric Isotope Effects Gauged by the Bowl-Inversion Barrier in Selectively Deuterated Pentaarylcorannulenes
  作者：Tomoharu Hayama、Kim K. Baldridge、Yao-Ting Wu、Anthony Linden、Jay S. Siegel

  DOI：10.1021/ja073052y

  日期：2008.2.6

  Motivated by a greater bowl depth and barrier to bowl inversion in sym-1,3,5,7,9-pentamanisylcorannulene compared to corannulene, an experimental plan is developed to measure the effective hydrogen/deuterium steric kinetic isotope effect (KIE). Symmetry arguments are used to design orthogonal isotope labeling patterns so that the barrier for the CD3 compound can be measured in the presence of the CH3 compound. This scheme eliminates the differential uncertainty in the temperature measurement by allowing both barriers to be measure in the same sample, which in turn reduces the error in determining the differential barrier. Ab initio computations corroborate the structure and isotope effect found experimentally. The predicted and determined steric KIE at 250 K is 1.08 (modified QUIVER at M06-2X/ cc-pVDZ) and 1.22 +/- 0.06 (VT-NMR), respectively. The results stem from differences in zero-point energy of the CH and CD motions; however, the phenomenology makes the CD3 group appear effectively "stickier" than CH3. The more the C-H center dot center dot center dot X interaction steepens the well, the "stickier" C-D should appear to be relative to C-H-an important consideration for molecular recognition and one supported by stronger binding constants for deuterated substrates.