1,4-di-tert-butylbenzene-d22 | 141708-53-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4-di-tert-butylbenzene-d22
• CAS: 141708-53-4
• 化学式: C₁₄H₂₂
• 分子量: 212.154
• InChiKey: OOWNNCMFKFBNOF-QSCUNVBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  2-氯-2-甲基丙烷-d9 、 氘代苯 在 三氯化铁 作用下， 生成 1,4-di-tert-butylbenzene-d22
  参考文献：
  名称：

  硫脲/ 1,4-二叔丁基苯包合物中客体和主体运动的氘核NMR和X射线晶体学研究

  摘要：

  Deuterium nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation times are used to investigate the guest and host molecular dynamics of solid 1,4-di-tert-butylbenzene-d4 (DTBB-d4), 1,4-di-tert-butylbenzene-d18 (DTBB-d18), the thiourea/ 1,4-di-tert-butylbenzene-d4 inclusion compound (TU/DTBB-d4), the thiourea/ 1,4-di-tert-butylbenzene-d22 inclusion compound (TU/DTBB-d22), the thiourea-d4/1,4-di-tert-butylbenzene inclusion compound (TU-d4/DTBB), and thiourea-d4 (TU-d4). X-ray crystallographic studies of TU/DTBB-d4 have been carried out at 291 K. In solid DTBB the phenyl ring is essentially static whereas the tert-butyl groups are undergoing rapid reorientation of both methyl and tert-butyl groups. Attempts to analyze the H-2 spectra and T1 data for DTBB-d18 suggest that the dynamics of the methyl and tert-butyl groups are nearly equivalent, and as a result, a satisfactory analysis, yielding methyl and tert-butyl rotational activation energies, was not possible. X-ray diffraction results for TU/DTBB-d4 suggest that, at 291 K, the phenyl ring is occupying three nearly equivalent sites. The H-2 NMR line shapes between 186 and 392 K were interpreted using a model in which the phenyl ring is rapidly flipping between three positions, with one position less favored, At 296 and 186 K the populations are 0.81:1.00:1.00 and 0.20:1.00.1.00, respectively. Relaxation times obtained between 111 and 322 K show no minimum, supporting the assumption of very rapid phenyl ring reorientation. For TU/DTBB-d22 a high-temperature T1 minimum is well-defined, and a second minimum, corresponding to tert-butyl group rotation, is reached at the lowest attainable temperatures. Line-shape simulations of the spectrum at 77 K yield methyl and tert-butyl group rotational rates of 1.0 x 10(3) and 2.0 x 10(6) s-1, respectively. Analysis of the higher temperature spectra (109-172 K) and T1 data (167-300 K) yield methyl rotation activation energies of 12.7 and 12.3 kJ/mol, respectively. Deuterium line-shape studies of the thiourea dynamics in TU-d4 and TU-d4/DTBB yield activation energies for 180-degrees flips about the C=S bond of 47 and 46 kJ/mol, respectively.

  DOI：

  10.1021/j100191a068